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dr hab. inż., prof. AGH
Magdziarz, Aneta
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Wydział Inżynierii Metali i Informatyki PrzemysłowejJednostki organizacyjne (rel.)
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- ArtykułOtwarty dostępValorisation of tyre waste from a vulcanisation plant by catalytic pyrolysis – Experimental investigations using pyrolysis–gas chromatography–mass spectrometry and drop-tube–fixed-bed reactor(2024) Jerzak, Wojciech; Wądrzyk, Mariusz; Sieradzka, Małgorzata; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThis study focuses on the use of car tyre waste collected at a tyre repair station in Krakow (Poland). Waste from damaged tyres is disposed of as municipal solid waste. Therefore, the management of waste tyres already shredded by pyrolysis at 500 °C has been proposed. Tyre waste was hypothesised to be converted into valuable chemical products by pyrolysis in a hybrid reactor (drop-tube–fixed-bed reactor). On a micro scale, pyrolysis–gas chromatography–mass spectrometry was used to analyse the pyrolysis process. It has been shown that the formation of aromatic hydrocarbons during pyrolysis clearly depends on whether the catalyst and tyre waste are mixed together or arranged in layers. Since the layered arrangement favoured the formation of hydrocarbons, such a system was used in the drop-tube–fixed-bed reactor. The high heating rate (500 °C/s) of tyre particles in the drop-tube–fixed-bed reactor at 500 °C allowed for the obtained a raw carbon black yield of 40.8 %. A similar yield of raw carbon black determined by thermogravimetric analysis for a heating rate of 0.17 °C/s) was observed at 800 °C. However, before commercial use, raw carbon black requires demineralisation because of its high ash content (approximately 50 %). The raw carbon black ash contained up to 90 % $SiO_{2}$, indicating that it could be a valuable catalyst material. Pyrolysis of tyre waste over the catalyst reduced the oxygen content in the oil and yield. The oil yields of tyre pyrolysis without a catalyst and over zeolite Y were 38 wt% and 35 wt%, respectively. The main components identified in the tyre pyrolysis gas were methane (27.6%), ethene (28.8%), and hydrogen (15.6%). The gas from catalytic pyrolysis was richer in CO and $CO_{2}$.
- ArtykułOtwarty dostępOat straw pyrolysis with ammonium chloride doping: Analysis of evolved gases, kinetic triplet, and thermodynamic parameters(2023) Jerzak, Wojciech; Gajek, Marcin; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThe purpose of this work was to determine the effect of the addition of $NH_{4}Cl$ to oat straw on the evolved gases, kinetic triplet, and thermodynamic parameters of the pyrolysis process at 873 K. A complementary approach allowed to assess the effects of the pyrolysis of chlorine- and nitrogen-enriched biomass. The thermal analysis of biomass was performed for four heating rates (5, 10, 20, and 30 K/min). The doping of $NH_{4}Cl$ in the straw favoured i) carbonisation of the chars, ii) formation of C–N bonds, iii) reduction of evolved $CH_{4}$ and $CO_{2}$, and iv) an increase in the mean values of the effective activation energy and all thermodynamic parameters. A group of reactions that best fit the experimental data of the pyrolysis process was selected. It was necessary to use unspecified mechanisms to describe the reaction model, particularly for samples enriched with $NH_{4}Cl$.
- ArtykułOtwarty dostępRelease of chlorine during oat straw pyrolysis doped with char and ammonium chloride(2023) Jerzak, Wojciech; Wądrzyk, Mariusz; Kalemba-Rec, Izabela; Bieniek, Artur; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejChlorine is one of the most undesirable elements in agricultural biomass which can cause operating problems during its thermal conversion. Even in low-temperature pyrolysis, chlorine is released in the gaseous phase. Therefore, in order to study the chlorine release during pyrolysis, the following samples were analyzed: oat straw, oat straw doped with char, oat straw doped with NH4Cl, and char doped with $NH_{4}Cl$. The pyrolysis process of these feedstocks was conducted at 400, 500 and 600°C under an inert atmosphere, with a short residence time (2 min) for a sample in the reactor. It transpired that the doping of ammonium chloride into oat straw increased the char yield. Doping oat straw with char as well as $NH_{4}Cl$ promoted biochar carbonization. Chlorine release was significantly inhibited when increasing the pyrolysis temperature from 400 to 600°C for samples of oat straw, oat straw doped with char, and oat straw doped with NH4Cl. In addition, despite the increase in pyrolysis temperature, the percentage of chlorine distributed into the gas phase decreased. Doping oat straw with $NH_{4}Cl$ had a positive effect on increasing the share of furfural (up to 12.9% at 400°C) in non-condensed gases identified by pyrolysis gas chromatography-mass spectrometry.
- ArtykułOtwarty dostępThe application of a drop-tube reactor for fast pyrolysis of agricultural biomass: an effective way to valuable products(2024) Bieniek, Artur; Sieradzka, Małgorzata; Wądrzyk, Mariusz; Jerzak, Wojciech; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThis paper presents experimental investigations of the fast pyrolysis of three agricultural biomass feedstocks in a drop-tube reactor (DTR) focusing on the production of bio-oil. Studying oat straw, corn straw, and rape straw allowed to optimize the use of diverse agricultural waste streams. The application of DTR with specially designed geometry and sample feeder gave information about pyrolysis conditions that can be helpful in the design of industrial-scale pyrolysis. The physical and chemical properties of feedstocks and received products using advanced instrumental techniques were determined. The yields of bio-oil were the highest during fast pyrolysis of studied biomass and were as follows: 53.2%, 51.28% and 49.11% for oat straw, corn straw and rape straw, respectively. The bio-oils were composed mainly of oxygen-containing compounds, with a dominant share of acids and phenols. It means that obtained bio-oils require upgrading their properties such as energy density and storage stability. The bio-chars were characterised by a high-energy density containing 60-70 wt.% carbon content giving carbon materials with a wide range of possible applications such as energy storage, absorbents and catalysts. The received pyrolytic gas was mostly composed of CO and CO2, and around 10% of hydrogen proving that it is possible to obtain pyrolysis-derived syngas as a source of energy. This research demonstrates the potential of using DTR for fast pyrolysis of agriculture residues aligning with the circular economy concept and contributing valuable knowledge for industrial applications.
- ArtykułOtwarty dostępMultifaceted analysis of products from the intermediate co-pyrolysis of biomass with Tetra Pak waste(2021) Jerzak, Wojciech; Bieniek, Artur; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThis study investigates the co-pyrolysis of two types of biomass (pine bark and wheat straw) with Tetra Pak waste (TPW). The experiments were performed using a fixed-bed reactor equipped with an innovative system, where a sample was rapidly heated to 600 °C before being rapidly cooled. The multifaceted analysis included the determination of the i) physical and chemical properties of the feedstocks and chars, ii) aqueous phase, tars, and waxes, iii) char ignition and burnout temperature, iv) chemical composition of gas, and v) distribution of carbon and hydrogen in the obtained products. The results showed that the addition of TPW to the both types of biomass significantly reduced the char mass and aqueous phase, decreased the carbon, hydrogen, and nitrogen contents of the char, and increased the wax and tar yields retained in the water cooler. Different organic compounds such as alkenes, aromatic hydrocarbons, and acids were found in tars and waxes. The chemical composition of the released gases was detected in situ (by a flue-gas analyser) and ex-situ (using gas chromatography). Changes in the concentrations of $H_{2}$, $CH_{4}$, $CO$, $CO_{2}$, and C2–C4 were observed. The addition of Tetra Pak to the two types of biomass had an evident and positive effect on the hydrogen content of the pyrolysis gas.
- ArtykułOtwarty dostępBenefits from co-pyrolysis of biomass and refuse derived fuel for biofuels production: experimental investigations(2024) Magdziarz, Aneta; Jerzak, Wojciech; Wądrzyk, Mariusz; Sieradzka, MałgorzataWydział Inżynierii Metali i Informatyki PrzemysłowejThe application of renewable fuels and waste for energy production is crucial environmentally and economically. Co-pyrolysis of biomass and refuse derived fuel (RDF) offers a promising pathway for valuable products that combine various benefits including enhanced energy recovery, waste valorisation, improved product quality, and environmental sustainability. Consideration of specific feedstocks and optimization of process parameters are necessary to maximise the efficiency and effectiveness of the co-pyrolysis process. This work presents investigations of the co-pyrolysis process of lignocellulosic biomass wastes (rye straw and agriculture grass) and RDF. These biomasses ensure efficient decomposition. The RDF, high in carbon (78.5 %) and hydrogen (11.8 %), was predominantly plastic based. Based on Py-GC-MS studies at 600°C, it was observed that the addition of RDF to biomass caused a significant decrease in the share of organic oxygen compounds among the released decomposition products. Laboratory tests were performed in a fixed-bed reactor for raw biomass and RDF and 1:1 and 3:1 biomass to RDF mass ratio. The results demonstrated that the yield of char production decreased with the addition of RDF, which promoted the bio-oil yield. Despite, RDF pyrolysis meets problems, it was proved that co-pyrolysis of biomass and RDF is a good solution for their utilization.
- ArtykułOtwarty dostępPotential of products from high-temperature pyrolysis of biomass and refuse-derived fuel pellets(2024) Jerzak, Wojciech; Mlonka-Mędrala, Agata; Gao, Ningbo; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThe management of energy contained in waste is an important research topic. Among many high-energy wastes, pellets are produced from refuse-derived fuels (RDF) and lignocellulosic biomass. This study investigated hightemperature pyrolysis (800 °C) of biomass and RDF pellets. Experiments were conducted in two reactors: i) on a microscale (thermogravimetric analysis) and ii) on a laboratory scale (fixed-bed reactor) to investigate the yields of the products (char, liquid fraction, and gas) and to characterise products toward their further application. The RDF char contained less carbon than the material before pyrolysis. The carbon content of the biomass char was 90%, almost twice that of the raw material. The biomass and RDF chars were chemically and physically activated to increase their specific surface areas. The chemically activated biomass char had a sorption capacity of 156.2 mg/CO2 at 25 °C and 0.1 MPa. The kinetics of CO2 sorption were also examined, and the maximum uptake was observed after 2–3 min. The higher heating value of the liquid phase, including the organic condensed phase, was 28.6 and 25.8 MJ/kg for pyrolysis of biomass and RDF pellets, respectively. The pyrolysis gas composition was analysed separately for the heating and isothermal processes. Due to the high CO, CH4, and H2 contents, the gas from the heating stage was characterised by a much higher heating value.
- ArtykułOtwarty dostępBiomass thermochemical conversion via pyrolysis with integrated CO2 capture(2020) Sieradzka, Małgorzata; Gao, Ningbo; Quan, Cui; Mlonka-Mędrala, Agata; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThe presented work is focused on biomass thermochemical conversion with integrated $CO_{2}$ capture. The main aim of this study was the in-depth investigation of the impact of pyrolysis temperature (500, 600 and 700 °C) and $CaO$ sorbent addition on the chemical and physical properties of obtained char and syngas. Under the effect of the pyrolysis temperature, the properties of biomass chars were gradually changed, and this was confirmed by examination using thermal analysis, scanning electron microscopy, X-ray diffraction, and porosimetry methods. The chars were characterised by a noticeable carbon content (two times at 700 °C) resulting in a lower O/C ratio. The calculated combustion indexes indicated the better combustible properties of chars. In addition, structural morphology changes were observed. However, the increasing pyrolysis temperature resulted in changes of solid products; the differences of char properties were not significant in the range of 500 to 700 °C. Syngas was analysed using a gas chromatograph. The following main components were identified: $CO$, $CO_{2}$, $CH_{4}$, $H_{2}$ and $C_{2}H_{4}$, $C_{2}H_{6}$, $C_{3}H_{6}$, $C_{3}H_{8}$. A significant impact of $CaO$ on $CO_{2}$ adsorption was found. The concentration of $CO_{2}$ in syngas decreased with increased temperature, and the highest decrease occurred in the presence of $CaO$ from above 60% to below 30% at 600 °C.
- ArtykułOtwarty dostępFast pyrolysis of agricultural biomass in drop tube reactor for bio-oil production: Numerical calculations(2023) Bieniek, Artur; Sieradzka, Małgorzata; Jerzak, Wojciech; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejFast biomass pyrolysis is an effective method for bio-oil production and can be performed in fluidised beds, augers, and drop-tube reactors. In this study, the fast pyrolysis of agricultural biomass (oat and corn straw) in a drop-tube reactor was investigated by applying multiparameter analysis involving numerical calculations. The main motivation for this analysis was to determine the operating parameters for fast pyrolysis under which the highest bio-oil production was achieved. In this study, the following operating parameters were involved: pyrolysis temperature (500 – 700 ◦C), volume flow rate of the carrier gas (3 – 5 l/min), mass flow rate of the feedstock (10 – 30 g/h), and diameter of the particle (250 – 750 μm). The analysis was performed using numerical methods with the Euler-Lagrange multiphase theory in a 2D axisymmetric model. According to the numerical results, selection of a particle size of 500 μm, pyrolysis temperature of 500 ◦C, and nitrogen flow rate of 3 l/min allows obtaining 51.16% and 52.09% of bio-oil for oat straw and corn straw pyrolysis, respectively. The biomass mass load did not influence the final product yield. The numerical results were successfully confirmed by experimental investigations where experiments supplied 53.2% and 51.3% of bio-oil to oat straw and corn straw, respectively.
- ArtykułOtwarty dostępPyrolysis of biomass wastes into carbon materials(2022) Sieradzka, Małgorzata; Kirczuk, Cezary; Kalemba-Rec, Izabela; Mlonka-Mędrala, Agata; Magdziarz, AnetaWydział Inżynierii Metali i Informatyki PrzemysłowejThis study presents the results of the biomass pyrolysis process focusing on biochar production and its potential energetic (as solid fuel) and material (as adsorbent) applications. Three kinds of biomass waste were investigated: wheat straw, spent coffee grounds, and brewery grains. The pyrolysis process was carried out under nitrogen atmosphere at 400 and 500 °C (residence time of 20 min). A significant increase in the carbon content was observed in the biochars, e.g., from 45% to 73% (at 400 °C) and 77% (at 500 °C) for spent coffee grounds. In addition, the structure and morphology were investigated using scanning electron microscopy. Thermal properties were studied using a simultaneous thermal analysis under an oxidising atmosphere. The chemical activation was completed using KOH. The sorption properties of the obtained biochars were tested using chromium ion $(Cr^{3+})$ adsorption from liquid solution. The specific surface area and average pore diameter of each sample were determined using the BET method. Finally, it was found that selected biochars can be applied as adsorbent or a fuel. In detail, brewery grains-activated carbon had the highest surface area, wheat straw-activated carbon adsorbed the highest amount of $Cr^{3+}$, and wheat straw chars presented the best combustion properties.