Volume 64, Issue 2

The efficiency of anaerobic digestion process is dependent on the type and composition of the material to be digested. This work examines the co-digestion of corn silage, beet pulp silage, carrot residues, and cheese whey in different configurations together with a glycerin fraction — the waste product of transestrification of oils (biodiesel production) in a 25 L bioreactor operated mesophically in a quasi-continuous mode. Co-digestion of corn silage with carrot residues appeared to be more effective than that with cheese whey resulting in the gas production rate equal to 5.9 L L−1 d−1 and 1.4 L L−1 d−1, respectively. The performed experiments showed that a combination of three substrates: corn silage, cheese whey, and glycerin fraction resulted in the highest methane content equal to 61 % and the biogas production rate of 1.8 L L−1 d−1.

Anoxic granulation process with four different inocula was monitored in a laboratory post-denitrification up-flow sludge bed (USB) reactor. Wastewater containing 20 mg L−1 NO3-N and methanol as an organic carbon source was used. Gradual increase of mass volumetric loading (B v) and hydraulic loading (γ) resulted in spontaneous granulation of anoxic biomass both from flocculant activated sludge and from anaerobic granulated sludge. With flocculant activated sludge as the inoculum, anoxic granules sedimentation properties and maximum loadings of the USB reactor depended on the sludge volume index (SVI) of the inoculum. B v,max achieved in the USB reactor with flocculant inoculum from a municipal wastewater treatment plant (SVI = 208 mL g−1) was only 4.2 kg of COD per m3 per day and 0.7 kg of NO3-N per m3 per day. B v,max using flocculant inoculum from an industrial wastewater treatment plant (SVI = 170 mL g−1) was 8.1 kg of COD per m3 per day and 1.35 kg of NO3-N per m3 per day. With anaerobic granulated inoculum (SVI range 8–11 mL g−1), markedly higher loadings in the USB reactor and lower SVI values of anoxic granulated biomass were achieved. Values of B v,max were in the range of 16.1–22.4 kg of COD per m3 per day and of 2.7–3.7 kg of NO3-N per m3 per day (depending on the inoculum and the granulation procedure). It was proved that anaerobic granulated sludge is not just an inoculum, it is also a carrier for new denitrification biomass.

Fouling and scaling are common phenomena that accompany membrane filtration and are caused by the presence of organic and inorganic matter in water, which may affect the removal of low-molecular mass organic micropollutants. Comparative filtration of deionized water containing selected phytoestrogens (biochanin A, daidzein, genistein, and coumestrol) was carried out using one new membrane and one contaminated with organic or inorganic matter. Two commercial Osmonics DS membranes were selected for the research, reverse osmosis DS3SE and nanofiltration DS5DK. Filtration was carried out in the dead-end mode. Higher removal of phytoestrogens was caused by reverse osmosis and retention depended on the molar mass of the compound. The decrease in membrane efficiency associated with fouling or scaling brings about an increase in the retention coefficient of phytoestrogens during both reverse osmosis and nanofiltration. The highest increase in phytoestrogen retention was found for the nanofiltraton membrane which was more susceptible to fouling than the osmotic one. This confirms the effect of membrane porosity on the phenomenon studied. The increase in micropollutants removal observed after fouling or scaling was caused by the modification of the membrane surface, hindered diffusion of the compound, and intensified or limited adsorption of micropollutants on the membrane surface.

The aim of this work was to investigate the displacement washing of kraft pulp manufactured from a blend of hardwoods. The experiments were carried out in a laboratory washing cell. In order to characterise the pulp fibres, the degree of freeness, kappa number, fibre length, as well as the specific volume and specific surface of swollen fibres were determined. The displacement washing process was described by displacement washing curves recorded for alkali lignin as a tracer. Mathematical treatment of the washing curves, obtained as a response to the step input signal, gave the Péclet number characterising the displacement of alkali lignin from the pulp pad. For detailed description of the displacement washing process, further parameters, such as the traditional wash yield, axial dispersion coefficient as well as the mean residence time and the space time were also evaluated. The results obtained for hardwood pulp were compared with those for softwood pulp published earlier. With respect to different chemical composition and morphological characteristics affecting both concentration of alkali lignin in mother liquor and physical properties of pulp pad, the displacement washing efficiency of hardwood pulp was found to be unambiguously greater in comparison with softwood pulp.

The aim of the research work was to investigate the effect of superficial gas velocity and solids concentration on the critical agitator speed, gas hold-up and averaged residence time of gas bubbles in an agitated gas-solid-liquid system. Experimental studies were conducted in a vessel of the inner diameter of 0.634 m. Different high-speed impellers: Rushton and Smith turbines, A 315 and HE 3 impellers, were used for agitation. The measurements were conducted in systems with different physical parameters of the continuous phase. Liquid phases were: distilled water (coalescing system) or aqueous solutions of NaCl (non-coalescing systems). The experiments were carried out at five different values of solids concentration and gas flow rate. Experimental analysis of the conditions of gas bubbles dispersion and particles suspension in the vessel with a flat bottom and four standard baffles showed that both gas and solid phases strongly affected the critical agitation speed necessary to produce a three-phase system. On the basis of experimental studies, the critical agitator speed for all agitators working in the gas-solid-liquid systems was found. An increase of superficial gas velocity caused a significant increase of the gas hold-up in both coalescing and non-coalescing three-phase systems. The type of the impeller strongly affected the parameters considered in this work. Low values of the critical impeller speed together with the relatively short average gas bubbles residence time tR in three phase systems were characteristic for the A 315 impeller. Radial flow Rushton and Smith turbines are high-energy consuming impellers but they enable to maintain longer gas bubbles residence time and to obtain higher values of the gas hold-up in the three-phase systems. Empirical correlations were proposed for the critical agitator speed, mean specific energy dissipated and the gas hold-up prediction. Its parameters were fitted using experimental data.

It is far more important how the cogeneration units are operated than whether they represent the latest technology progress or not. Therefore, for the management of cogeneration units it is a key issue to find optimal operating conditions bringing in the largest income. This may be achieved by combined marginal and overall performance criteria application. To prove this statement, two cogeneration units operating in the Slovak Republic, marked as A and B, were examined. Both of them use the liberal market environment and participate in provisioning ancillary services. Marginal profit values without and with ancillary services provisioning clearly indicate the most advantageous base load value, which is in both cases in the middle of the load regulation range. As shown, together with the total profit function, they are very suitable indicators of the optimal load location and a flexible tool for the market situation evaluation. Heat delivery capability of B to customers reaches its maximum at the middle of the load regulation range, again reinforcing the optimal part load operation. Being equipped with supplementary firing, the marginal steam production of B was found to be higher than 100 % which confirms that the rules for marginal quantities values are not as strict as those for overall and specific quantities.

Pyrolysis of a wood chips mixture and main wood compounds such as hemicellulose, cellulose and lignin was investigated by thermogravimetry. The investigation was carried out in inert nitrogen atmosphere with temperatures ranging from 20°C to 900°C for four heating rates: 2 K min−1, 5 K min−1, 10 K min−1, and 15 K min−1. Hemicellulose, cellulose, and lignin were used as the main compounds of biomass. TGA and DTG temperature dependencies were evaluated. Decomposition processes proceed in three main stages: water evaporation, and active and passive pyrolysis. The decomposition of hemicellulose and cellulose takes place in the temperature range of 200–380°C and 250–380°C, while lignin decomposition seems to be ranging from 180°C up to 900°C. The isoconversional method was used to determine kinetic parameters such as activation energy and pre-exponential factor mainly in the stage of active pyrolysis and partially in the passive stage. It was found that, at the end of the decomposition process, the value of activation energy decreases. Reaction order does not have a significant influence on the process because of the high value of the pre-exponential factor. Obtained kinetic parameters were used to calculate simulated decompositions at different heating rates. Experimental data compared with the simulation ones were in good accordance at all heating rates. From the pyrolysis of hemicellulose, cellulose, and lignin it is clear that the decomposition process of wood is dependent on the composition and concentration of the main compounds.

The present study deals with numerical simulations of turbulent flow of a liquid-liquid system in a Kenics static mixer with ten inserts. CFD approach was used in two modes: large eddy simulation (LES) and unsteady Reynolds averaged Navier-Stokes (URANS). Large eddy simulation in the static mixer was carried out using the dynamic kinetic energy subgrid-scale model with standard wall functions whereas in URANS approach the standard k-ɛ turbulent model and standard wall functions were applied. Two-phase flow was modelled employing the “mixture model” of the Eulerian type. The simulations were performed mainly for the Reynolds number of 10000 with the volumetric ratio of 99 % of water to 1 % of oil. The investigations revealed that due to distinct distributions of the turbulence measures, the drop breakup process occurs with varying intensity in different locations within the mixer inserts. Significantly higher local values of the dissipation rate, ɛ, were predicted in URANS than in LES. However, both modelling methods indicated high values of ɛ at the beginning and the end of the mixer inserts, which implies the maximum shearing action exerted on the drops. Consequently, the inflow and outflow zone of each insert are the regions of the highest breakup intensity.

Modelling and simulation of hybrid reactive separation system in steady state and in dynamic regime was carried out. The investigated hybrid process consisted of a reactive distillation column and a pervaporation membrane located in the distillate stream to remove water from the process. Heterogeneously catalysed esterification of propionic acid with propan-1-ol to propyl propionate and water was chosen as the model chemical reaction. Esterification reactions are a typical example of equilibrium-limited reactions producing water as a by-product. Using just a pervaporation membrane brings the biggest benefit in increasing the yield of one of the reactants due to the removal of water. To study reactive separation processes, a model of the hybrid system in steady state and in dynamic regime was developed. Steady state behaviour of the model was studied for different hybrid system configurations. The effect of catalyst amount doubling was also investigated. Dynamic behaviour of the system during the step changes of propionic acid feed flow rate and during the membrane module failure was investigated. For this reason, the conversion of propionic acid, purity of the product stream, mole fraction of water, and the temperature in three different parts of the reactive distillation column were monitored.

The main purpose of the paper is to apply the large eddy simulations (LES) technique and to verify its use as a predicting tool for turbulent liquid-liquid flow in an SMX static mixer. LES modeling was carried out using the Smagorinsky-Lilly model of the turbulent subgrid viscosity for the Reynolds number of 5000 and 10000. The continuous phase was water and the dispersed phase was silicon oil. The investigation covers the effects of the density ratio between the phases. Three different cases of liquid densities were considered. The dispersed phase concentration distribution in the mixer cross-sections was compared with the corresponding time averaged results obtained formerly for the same configuration in a steady-state simulation using the standard RANS approach with the k-ɛ model. The dependency of the standard deviation of the dispersed phase concentration on the distance from the mixer inlet and the impact of the centrifugal force on the phase concentration distribution were investigated. The presented results for the SMX static mixer confirm conclusions of previous studies by Jaworski et al. (2006) obtained for a Kenics static mixer and show less a pronounced influence of the centrifugal force on the phase concentration distribution of the LES results in comparison to the RANS case.

Simulation of a hybrid fermentation-separation process for the production of butyric acid (BA) based on published data was done. A unit consisting of a bioreactor with immobilized cells in the fibrous bed and of separation by pertraction through supported liquid membranes (SLM) was considered. Productivities of the unit volume of a fixed bed bioreactor in continuous and fed-batch fermentation at pH 5.5 and 6.0 were used. Concentration of BA in the bioreactor outlet stream was assumed to be in the interval from 0.11 kmol m−3 to 0.45 kmol m−3. Data on the pertraction through SLM with phosphonium ionic liquid (IL) and bulk liquid membrane with trioctylamine (TOA) as carriers were used. A strong increase in the required membrane area was found for both carriers at the pH of pertraction above 4. pH values of fermentation and pertraction should be optimized independently. It is advantageous to have pH of the feed into the pertraction unit of about 4. Dependences of the membrane area on the pertraction efficiency are nearly linear and not very sharp, especially for IL, what enables working at the pertractor efficiency exceeding 90 %. Application of phosphonium IL is promising compared to classical extractant TOA because of lower demand of the membrane area in a large interval of BA concentrations in the pertractor feed.

Aeration of municipal landfills contributes to the acceleration of organic matter degradation and to the decrease of pollutant emission into air, water, and soil. Biodegradation of organic matter present in municipal waste, deposited in a landfill, by microorganisms under anaerobic conditions is a slow process. The aim of the study was to carry out simulations of an aerobic landfill in lysimeters, to determine the influence of aeration rate on the degradation of organic matter present in landfills, and to formulate a mathematical model defining the changes of carbon content in leachate and in gas produced. In this work, simulation of aerobic landfill leachate degradation was carried out in laboratory scale lysimeters with the working volume of 15 L. The changes of BOD5, COD, and ammonium nitrogen concentration during aeration were similar for all aeration rates. During aeration, the BOD5 index decreased by 99.9 %, COD decreased by 95.1 %, and ammonium nitrogen concentration by 93 %. The proposed kinetic model defines the processes of organic carbon content changes in simulated leachate and the quantity of carbon dioxide for aerobic landfill simulation quite well.

An anoxic fixed film bioreactor (FFB) with biomass immobilized on activated carbon and an aerobic continuous stirred tank bioreactor with overflow were applied to degrade concentrate from nanofiltration of real textile effluents containing Reactive Red 120 (RR-120). The efficiency of color removal was 99 % irrespective of the fraction of nanofiltration concentrate in the feed. An approximate dye balance based on the assessed adsorption capacity of RR-120 by activated carbon indicated that the dye was removed by means of adsorption as well as of biological processes. Aromatic amine released from a dye molecule was fully adsorbed by activated carbon. COD level in the outflow of the system was above that imposed by legislation. Despite an adjustment of the feed pH to 7 this was constantly increasing up to the value above 9 in both reactors. Neither the nanofiltration concentrate nor the effluents from the bioreactors affected the growth of Pseudomonas putida used as toxicity indicator.

Kinetics and efficiency of Fenton’s and ozonation processes for the pretreatment of two landfill leachates (fresh and mature) resulting from municipal waste disposal were studied. Both samples presented high organic load, high toxicity and low biodegradability. These were the reasons why oxidative treatment was proposed. Fresh and mature leachate showed different behaviors in the oxidation experiments. The final extents of removal were attained in comparable time intervals in both oxidation systems. Maximal removal of organics by the Fenton’s oxidation reached more than 50 % according to COD. Zero or first order kinetics were found the best to describe the organic components (in terms of COD and DOC) removal by the Fenton’s oxidation for both landfill leachates. Higher reaction rate values of the Fenton’s oxidation were achieved with fresh leachate samples. The efficiency of initial organics removal with ozone was about 70 % for mature leachate, while in case of the fresh one only 41 % of COD were removed. The best fits of COD and DOC experimental data from oxidation of fresh and mature leachates were obtained by a combined kinetic model. No significant improvement of the biodegradability of landfill leachates was achieved using these treatment procedures. Regarding toxicity, ozonation showed to be more effective than the Fenton’s oxidation. Advanced oxidation experiments confirmed that the Fenton’s oxidation and ozonation are comparable oxidative treatment techniques for the reduction of organic pollution in the investigated municipal landfill leachates. However, neither of them is effective enough to be used as a pretreatment method followed by biological treatment.

Structural foam moldings, composed of three co-axial cylinders differing in diameter (10 mm, 20 mm, and 30 mm) and length, were produced from isotactic polypropylene (PP) and 0.5 mass % 1,1′-azobisformamide on an in-line injection molding machine in a mould cavity pre-pressurized with nitrogen by the classical low-pressure process combined with egression of foamed melt from the core. Injection-molding conditions were as follows: melt temperature, 220°C, mold temperature, 20°C, cooling time, 5 min, gas-counter pressure, 0.5 MPa. The sprue gate was at the end of the smallest cylinder and its diameter was varied from 4 mm to 7 mm. To investigate the development of β-PP modification in terms of phenomena due to the phase change in the mould cavity (expansion), appropriate specimens (cross-sections) were cut from the middle of each cylinder in parallel and perpendicular orientation to the flow direction and were investigated by WAXS, DSC, and POM. As revealed by WAXS, β-PP is present in all cylinders, always concentrated in certain regions of the cross-section — mainly in the surface layers of the smallest cylinder (D1) and in the foamed core of the other two cylinders (D2 and D3). Its concentration was found to change with the sprue dimensions. High β-PP concentration is associated with a preferred orientation in the skin of the smallest cylinder and with better expansion conditions in larger cylinders. Presence of the β-phase in the surface layers and in the core of the moldings was proved by DSC and POM.

A study on the effect of the metal-support interaction by employing iron particles supported on magnesium oxide (MgO) nanopowder in an alcohol-CVD process for single-walled carbon nanotubes growth is presented. Upon the prolongation of the process time, three main observations were detected: (i) decrease of the mean nanotubes diameter, (ii) reduction of the diameter distribution by the factor of two, (iii) increase of relative purity of the samples.

Enzymatic synthesis of ethyl lactate was studied in organic solvents and in ionic liquids to determine optimal media for the reaction, and to investigate the effect of water content on the ester yield. Experiments proved that Cyphos 202 ionic liquid is the best solvent affording the highest ethyl lactate yields. Furthermore, 20 times less enzyme sufficed to carry out the reaction in this ionic liquid compared to organic solvents; ionic liquid could be applied as solvent. Using water removal, the ester yield decreased since a side reaction, dimerization of lactic acid, occurred as well. In contrast to these results, without water removal, the produced water was partly consumed by the decomposition of lactoyllactic acid to free lactic acid, increasing thus the substrate concentration of the mixture and enhancing the ester yield.

To carry out autothermal drying processes during the composting of biomass, a horizontal tubular reactor was designed and tested. A biodrying tunnel of the total capacity of 240 dm3 was made of plastic material and insulated with polyurethane foam to prevent heat losses. Municipal solid waste and structural plant material were used as the input substrate. As a result of autothermal drying processes, moisture content decreased by 50 % of the initial moisture content of organic waste of about 800 g kg−1. In the tested cycles, high temperatures of biodried waste mass were achieved (54–56°C). An appropriate quantity of air was supplied to maintain a satisfactory level of temperature and moisture removal in the biodried mass and high energy content in the final product. The heat of combustion of dried waste and its calorific value were determined in a calorimeter. Examinations of pyrolysis and gasification of dried waste confirmed their usefulness as biofuel of satisfactory energy content.

Nitrogen oxides are nowadays a subject of global concern. Several types of nitrogen oxides exist in the environment: N2O, NO, NO2, N2O3, N2O4, N2O5. The abbreviation NOx usually relates to nitric oxide NO, nitrogen dioxide NO2, and nitrous oxide N2O. The first two are harmful pollutants for both environment and human health, whereas the third is one of the greenhouse gases. Implementation of stringent NOx emission regulations requires the development of new NOx removal technologies from exhaust gases. One of many proposals for NOx emission reduction is the application of an oxidizing agent which would transform NOx to higher nitrogen oxides with higher solubility in water. The main objective of the paper was to present the rate constant of nitric oxide oxidation, determined in our studies.