Marek Klein

Effective method of treatment of effluents from production of bitumens under basic pH conditions using hydrodynamic cavitation aided by external oxidants

Utilization of cavitation in advanced oxidation processes (AOPs) is a promising trend in research on treatment of industrial effluents. The paper presents the results of investigations on the use of hydrodynamic cavitation aided by additional oxidation processes (O3/H2O2/Peroxone) to reduce the total pollution load in the effluent from the production of bitumens. A detailed analysis of changes in content of volatile organic compounds (VOCs) for all processes studied was also performed. The studies revealed that the most effective treatment process involves hydrodynamic cavitation aided by ozonation (40% COD reduction and 50% BOD reduction). The other processes investigated (hydrodynamic cavitation+H2O2, hydrodynamic cavitation+Peroxone and hydrodynamic cavitation alone) ensure reduction of COD by 20, 25 and 13% and reduction of BOD by 49, 32 and 18%, respectively. The results of this research revealed that most of the VOCs studied are effectively degraded. The formation of byproducts is one of the aspects that must be considered in evaluation of the AOPs studied. This work confirmed that furfural is one of the byproducts whose concentration increased during treatment by hydrodynamic cavitation alone as well as hydrodynamic cavitation aided by H2O2 as an external oxidant and it should be controlled during treatment processes.

The emissions of monoaromatic hydrocarbons from small polymeric toys placed in chocolate food products

The article presents findings on the emissions of selected monoaromatic hydrocarbons from childrens toys placed in chocolate food products. The emission test system involved the application of a new type of microscale stationary emission chamber, μ-CTE™ 250. In order to determine the type of the applied polymer in the manufacture of the tested toys, Fourier transform infrared spectroscopy and thermogravimetric analysis coupled with differential scanning calorimetry were used. It was found that the tested toy components or the whole toys (figurines) are made of two main types of polymers: polyamide and acrylonitrile-butadiene-styrene copolymer. Total number of studied small polymeric toys was 52. The average emissions of selected monoaromatic hydrocarbons from studied toys made of polyamide were as follows: benzene: 0.45 ± 0.33 ng/g; toluene: 3.3 ± 2.6 ng/g; ethylbenzene: 1.4 ± 1.4 ng/g; p,m-xylene: 2.5 ± 4.5 ng/g; and styrene: 8.2 ± 9.9 ng/g. In the case of studied toys made of acrylonitrile-butadiene-styrene copolymer the average emissions of benzene, toluene, ethylbeznene, p,m-xylene and styrene were: 0.31 ± 0.29 ng/g; 2.5 ± 1.4 ng/g; 4.6 ± 8.9 ng/g; 1.4 ± 1.1 ng/g; and 36 ± 44 ng/g, respectively.

Structure, Mechanical, Thermal and Fire Behavior Assessments of Environmentally Friendly Crude Glycerol-Based Rigid Polyisocyanurate Foams

In this work, rigid polyisocyanurate foams were prepared at partial substitution (0–70 wt%) of commercially available petrochemical polyol, with previously synthesized biopolyol based on crude glycerol and castor oil. Influence of the biopolyol content on morphology, chemical structure, static and dynamic mechanical properties, thermal insulation properties, thermal stability and flammability was investigated. Incorporation of 35 wt% of crude glycerol-based polyol had reduced average cell size by more than 30% and slightly increased closed cell content, simultaneously reducing thermal conductivity coefficient of foam by 12% and inhibiting their thermal aging. Applied modifications showed also positive impact on the mechanical performance of rigid foams. Increase of crosslink density resulted in enhancement of compressive strength by more than 100%. Incorporation of prepared biopolyol resulted in enhancement of thermal stability and changes in degradation pathway. Up to 35 wt% share of crude glycerol-based polyol, foams showed similar flammability as reference sample, which can be considered very beneficial from the environmental point of view.

Foamed Polyurethane Composites With Different Types of Ash – Morphological, Mechanical and Thermal Behavior Assessments

Incorporation of two types of ash particles into flexible polyurethane foams has been investigated, wood ash from gasification process and fly ash resulting from coal burning in power plant. Samples were modified with 5, 10 and 15 wt% of fillers. Structure, mechanical and thermal properties of obtained foams were investigated. Incorporation of both types of ash particles resulted in materials showing satisfactory mechanical properties, simultaneously decreasing their density. Addition of fly ash inhibited noticeably thermal degradation of material, because of the thermal insulation effect of gas trapped in the spherical ash particles. Results of research show that fly ash can be successfully used as a modifier of thermal properties in polyurethane foams, enhancing the economical aspect of the production through the decrease of materials density and incorporation of low cost filler.

Utilization of shale cuttings in production of lightweight aggregates

The development of technologies for unconventional hydrocarbon exploration requires designing procedures to manage drilling waste that are consistent with the waste management hierarchy. In view of this, the possibility to apply shale drill cuttings as a prospective additive (replacing bentonite) to fly ash used for the production of lightweight aggregates (LWAs) was investigated. Moreover, a facile, waste-free method of LWAs production with using shales was proposed. Cuttings were characterized in terms of their mineralogical and elemental composition (XRD and XRF) as well as thermophysical behavior (TG-DTA and fusibility test). The sintered product, in turn, was assessed taking into account its structure, physicochemical and mechanical properties. It was found that the composition of the shale drill cuttings meets the conditions required for the bloating (as expressed by the SiO2/ΣFlux and Al2O3/SiO2 ratios) and binding processes (Al2O3 content), essential for the aggregates production. In comparison to bentonite, shales provided an additional source of kaolinite, which thermal transformation to mullite is crucial for the formation of mechanically durable structure of the aggregate. Moreover, the bulk density of the sintered product was found to be less than 1200 kg/m3, and the dry particle density below 2000 kg/m3, confirming that the obtained porous material belong to lightweight aggregates with accordance to European standard (UNE-EN-13055-1). The porosity of LWA was found to be higher (even up to 50%), thus the apparent density lower, compared with the reference product containing bentonite. These properties were accompanied by the relatively high crushing resistance which was up to 4.4 N/mm2. Hereby, usefulness of shale drill cuttings for LWAs production was confirmed.

Structure and performance properties of environmentally-friendly biocomposites based on poly(ɛ-caprolactone) modified with copper slag and shale drill cuttings wastes

The potential application of two types of industrial wastes, drill cuttings (DC) and copper slag (CS), as silica-rich modifiers of poly(ɛ-caprolactone) (PCL) was investigated. Chemical structure and physical properties of DC and CS fillers were characterized using X-ray diffractometer, X-ray fluorescence spectroscopy, particle size and density measurements. PCL/DC and PCL/CS composites with a variable content of filler (5 to 50 parts by weight) were prepared by melt compounding in an internal mixer. It was observed that lower particle size of DC filler enhanced processing of biocomposites comparing to CS filler. Smaller particles of DC filler and thus the higher specific surface area, enabled better encapsulation of filler by polymer chains, hence lower porosity and consequently higher tensile properties comparing to PCL/CS biocomposites. It was noticed, that the impact of waste filler characteristics on tensile properties became negligible at higher loadings. This indicates weak interactions between waste filler and PCL matrix, due to aggregation of filler particles and formulation of voids in phase boundary. This phenomenon was confirmed by scanning electron microscopy, headspace analysis and thermogravimetric analysis. Microbial tests revealed that prepared biocomposites show no toxic effect towards analyzed bacterial strains, therefore could be considered as environmentally-friendly.

Two-step Conversion of Crude Glycerol Generated by Biodiesel Production into Biopolyols: Synthesis, Structural and Physical Chemical Characterization

In this work biopolyols were synthesized via two-step process from crude glycerol and castor oil. For better evaluation of analyzed process, the impact of its time and temperature on the structure and properties of biopolyols was determined. Obtained results fully justified conducting of synthesis in two steps. Prepared materials were characterized by hydroxyl value and water content comparable to polyols industrially applied in manufacturing of polyurethane materials. Synthesized biopolyols were characterized in terms of their chemical structure using spectroscopic techniques: Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance spectroscopy. Obtained data confirmed the influence of synthesis’ parameters on the chemical structure of prepared biopolyols and correlated with their other parameters. On both stages of reaction, collected by-products were also analyzed with FTIR spectroscopy.

Performance properties of rigid polyurethane-polyisocyanurate/brewers’ spent grain foamed composites as function of isocyanate index

Abstract In the presented work, rigid polyurethane-polyisocyanurate (PUR-PIR) foams filled with brewers’ spent grain (BSG) were prepared. The influence of the isocyanate index (II) on its performance was investigated. Foams obtained with higher isocyanate index required a higher amount of hydrofluorocarbon physical blowing agent to provide the same apparent density of material. An increase of isocyanate index resulted in a slight decrease of cell size, which was related to the increased crosslink density due to enhanced generation of allophanate and biuret groups. Deterioration of compressive strength, from 226 to 202 kPa was observed with the rise of the isocyanate index. Dynamic mechanical analysis and swelling tests confirmed the increase of crosslink density with the increasing isocyanate index. The glass transition temperature rose from 165.7°C to 193.2°C. Fourier transform infrared (FTIR) analysis indicated an increase of the isocyanurate rings’ content in composites with a higher isocyanate index, causing noticeable enhancement of thermal stability. The onset of degradation was shifted from 196°C to 211°C.