Search results for: pyrolysis gasification

Authors: M. Mashiur Rahman, Ulrik Birk Henriksen, Jesper Ahrenfeldt, Maria Puig Arnavat

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Using biomass gasification to make producer gas is one of the promising sustainable energy options available for small scale plant and rural applications for power and electricity. Tar content in producer gas is the main problem if it is used directly as a fuel. A low-tar biomass (LTB) gasifier of approximately 30 kW capacity has been developed to solve this. Moving bed gasifier with internal recirculation of pyrolysis gas has been the basic principle of the LTB gasifier. The gasifier focuses on the concept of mixing the pyrolysis gases with gasifying air and burning the mixture in separate combustion chamber. Five tests were carried out with the use of wood pellets and wood chips separately, with moisture content of 9-34%. The LTB gasifier offers excellent opportunities for handling extremely low-tar in the producer gas. The gasifiers producer gas had an extremely low tar content of 21.2 mg/Nm³ (avg.) and an average lower heating value (LHV) of 4.69 MJ/Nm³. Tar content found in different tests in the ranges of 10.6-29.8 mg/Nm³. This low tar content makes the producer gas suitable for direct use in internal combustion engine. Using mass and energy balances, the average gasifier capacity and cold gas efficiency (CGE) observed 23.1 kW and 82.7% for wood chips, and 33.1 kW and 60.5% for wood pellets, respectively. Average heat loss in term of higher heating value (HHV) observed 3.2% of thermal input for wood chips and 1% for wood pellets, where heat loss was found 1% of thermal input in term of enthalpy. Thus, the LTB gasifier performs better compared to typical gasifiers in term of heat loss. Equivalence ratio (ER) in the range of 0.29 to 0.41 gives better performance in terms of heating value and CGE. The specific gas production yields at the above ER range were in the range of 2.1-3.2 Nm³/kg. Heating value and CGE changes proportionally with the producer gas yield. The average gas compositions (H₂-19%, CO-19%, CO₂-10%, CH₄-0.7% and N₂-51%) obtained for wood chips are higher than the typical producer gas composition. Again, the temperature profile of the LTB gasifier observed relatively low temperature compared to typical moving bed gasifier. The average partial oxidation zone temperature of 970°C observed for wood chips. The use of separate combustor in the partial oxidation zone substantially lowers the bed temperature to 750°C. During the test, the engine was started and operated completely with the producer gas. The engine operated well on the produced gas, and no deposits were observed in the engine afterwards. Part of the producer gas flow was used for engine operation, and corresponding electrical power was found to be 1.5 kW continuously, and maximum power of 2.5 kW was also observed, while maximum generator capacity is 3 kW. A thermodynamic equilibrium model is good agreement with the experimental results and correctly predicts the equilibrium bed temperature, gas composition, LHV of the producer gas and ER with the experimental data, when the heat loss of 4% of the energy input is considered.

Keywords: biomass gasification, low-tar biomass gasifier, tar elimination, engine, deposits, condensate

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Authors: Kianoosh Shojae

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In recent years, the environmental challenges due to the excessive use of fossil fuels have led to heightened greenhouse gas production. In response, biodiesel has emerged as a cleaner alternative, offering reduced pollutant emissions compared to traditional fuels. The large-scale production of biodiesel, involving ester exchange of animal fats or vegetable oils, results in a surplus of crude glycerin. With environmental regulations on the rise and an increasing demand for biodiesel, glycerin production has seen a significant upswing. This paper focuses on the economic significance of glycerin through its pyrolysis as a raw material, particularly in the synthesis of metals. As industries pivoted towards cleaner fuels, glycerin, as a byproduct of biodiesel production, is poised to remain a cost-effective and surplus product. In this work, for evaluating the possible performance of using the gaseous products from the pyrolysis reaction of glycerol, we concerned the glycerin pyrolysis reactions, emphasizing the catalytic role of activated carbon, various reaction pathways and the impact of carrier gas flow rate on hydrogen production, providing valuable insights into the evolving landscape of sustainable fuel alternatives.

Keywords: biodiesel, glycerin pyrolysis, activated carbon catalysis, syngas

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Authors: Jaroslav Frantík, Jan Najser

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This article deals with increasing the energy efficiency of a plant in terms of optimizing the process. The European Union is striving to achieve the climate-energy package in the area increasing of energy efficiency. The goal of energy efficiency is to reduce primary energy consumption by 20% within the EU until 2020. The objective of saving energy consumption in the Czech Republic was set at 47.84 PJ (13.29 TWh). For reducing electricity consumption, it is possible to choose: a) mandatory increasing of energy efficiency, b) alternative scheme, c) combination of both actions. The Czech Republic has chosen for reducing electricity consumption using-alternative scheme. The presentation is focused on the proposal of a technological unit dealing with the gasification process of processing of biomass with an increase of power in the output. The synthesis gas after gasification of biomass is used as fuel in a cogeneration process of reciprocating internal combustion engine with the classic production of heat and electricity. Subsequently, there is an explanation of the ORC system dealing with the conversion of waste heat to electricity with the using closed cycle of the steam process with organic medium. The arising electricity is distributed to the power grid as a further energy source, or it is used for needs of the partial coverage of the technological unit. Furthermore, there is a presented schematic description of the technology with the identification of energy flows starting from the biomass treatment by drying, through its conversion to gaseous fuel, producing of electricity and utilize of thermal energy with minimizing losses. It has been found that using of ORC system increased the efficiency of the produced electricity by 7.5%.

Keywords: biomass, efficiency, gasification, ORC system

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Authors: Bhargav Baruah, Ali Shemsedin Reshad, Pankaj Tiwari

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This work presents a detailed study on the thermal degradation kinetics of co-pyrolysis of oil shale of Upper Assam, India with rubber seed shell, and lab-scale pyrolysis to investigate the influence of pyrolysis parameters on product yield and composition of products. The physicochemical characteristics of oil shale and rubber seed shell were studied by proximate analysis, elemental analysis, Fourier transform infrared spectroscopy and X-ray diffraction. The physicochemical study showed the mixture to be of low moisture, high ash, siliceous, sour with the presence of aliphatic, aromatic, and phenolic compounds. The thermal decomposition of the oil shale with rubber seed shell was studied using thermogravimetric analysis at heating rates of 5, 10, 20, 30, and 50 °C/min. The kinetic study of the oil shale pyrolysis process was performed on the thermogravimetric (TGA) data using three model-free isoconversional methods viz. Friedman, Flynn Wall Ozawa (FWO), and Kissinger Akahira Sunnose (KAS). The reaction mechanisms were determined using the Criado master plot. The understanding of the composition of Indian oil shale and rubber seed shell and pyrolysis process kinetics can help to establish the experimental parameters for the extraction of valuable products from the mixture. Response surface methodology (RSM) was employed usinf central composite design (CCD) model to setup the lab-scale experiment using TGA data, and optimization of process parameters viz. heating rate, temperature, and particle size. The samples were pre-dried at 115°C for 24 hours prior to pyrolysis. The pyrolysis temperatures were set from 450 to 650 °C, at heating rates of 2 to 20°C/min. The retention time was set between 2 to 8 hours. The optimum oil yield was observed at 5°C/min and 550°C with a retention time of 5 hours. The pyrolytic oil and gas obtained at optimum conditions were subjected to characterization using Fourier transform infrared spectroscopy (FT-IR) gas chromatography and mass spectrometry (GC-MS) and nuclear magnetic resonance spectroscopy (NMR).

Keywords: Indian oil shale, rubber seed shell, co-pyrolysis, isoconversional methods, gas chromatography, nuclear magnetic resonance, Fourier transform infrared spectroscopy

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Authors: Vera Marcantonio, Marcello De Falco, Mauro Capocelli, Álvaro Amado-Fierro, Teresa A. Centeno, Enrico Bocci

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Concerns about energy security, energy prices, and climate change led scientific research towards sustainable solutions to fossil fuel as renewable energy sources coupled with hydrogen as an energy vector and carbon capture and conversion technologies. Among the technologies investigated in the last decades, biomass gasification acquired great interest owing to the possibility of obtaining low-cost and CO₂ negative emission hydrogen production from a large variety of everywhere available organic wastes. Upstream and downstream treatment were then studied in order to maximize hydrogen yield, reduce the content of organic and inorganic contaminants under the admissible levels for the technologies which are coupled with, capture, and convert carbon dioxide. However, studies which analyse a whole process made of all those technologies are still missing. In order to fill this lack, the present paper investigated the coexistence of hydrothermal carbonization (HTC), sorption enhance gasification (SEG), hot gas cleaning (HGC), and CO₂ conversion by dielectric barrier discharge (DBD) plasma reactor for H₂ production from biomass waste by means of Aspen Plus software. The proposed model aimed to identify and optimise the performance of the plant by varying operating parameters (such as temperature, CaO/biomass ratio, separation efficiency, etc.). The carbon footprint of the global plant is 2.3 kg CO₂/kg H₂, lower than the latest limit value imposed by the European Commission to consider hydrogen as “clean”, that was set to 3 kg CO₂/kg H₂. The hydrogen yield referred to the whole plant is 250 gH₂/kgBIOMASS.

Keywords: biomass gasification, hydrogen, aspen plus, sorption enhance gasification

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Authors: Thomas Arink, Isam Janajreh

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The petroleum industry generates significant amounts of waste in the form of drill cuttings, contaminated soil and oily sludge. Drill cuttings are a product of the off-shore drilling rigs, containing wet soil and total petroleum hydrocarbons (TPH). Contaminated soil comes from different on-shore sites and also contains TPH. The oily sludge is mainly residue or tank bottom sludge from storage tanks. The two main treatment methods currently used are incineration and thermal desorption (TD). Thermal desorption is a method where the waste material is heated to 450ºC in an anaerobic environment to release volatiles, the condensed volatiles can be used as a liquid fuel. For the thermal desorption unit dry contaminated soil is mixed with moist drill cuttings to generate a suitable mixture. By thermo gravimetric analysis (TGA) of the TD feedstock it was found that less than 50% of the TPH are released, the discharged material is stored in landfill. This study proposes co-gasification of petroleum waste with waste tires as an alternative to thermal desorption. Co-gasification with a high-calorific material is necessary since the petroleum waste consists of more than 60 wt% ash (soil/sand), causing its calorific value to be too low for gasification. Since the gasification process occurs at 900ºC and higher, close to 100% of the TPH can be released, according to the TGA. This work consists of three parts: 1. a mathematical gasification model, 2. a reactive flow CFD model and 3. experimental work on a drop tube reactor. Extensive material characterization was done by means of proximate analysis (TGA), ultimate analysis (CHNOS flash analysis) and calorific value measurements (Bomb calorimeter) for the input parameters of the mathematical and CFD model. The mathematical model is a zero dimensional model based on Gibbs energy minimization together with Lagrange multiplier; it is used to find the product species composition (molar fractions of CO, H2, CH4 etc.) for different tire/petroleum feedstock mixtures and equivalence ratios. The results of the mathematical model act as a reference for the CFD model of the drop-tube reactor. With the CFD model the efficiency and product species composition can be predicted for different mixtures and particle sizes. Finally both models are verified by experiments on a drop tube reactor (1540 mm long, 66 mm inner diameter, 1400 K maximum temperature).

Keywords: computational fluid dynamics (CFD), drop tube reactor, gasification, Gibbs energy minimization, petroleum waste, waste tires

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Authors: María del Carmen Recio-Ruiz, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol, Tomás Cordero

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Nowadays, fossil resources are main precursors for fuel production. Due to their contribution to the greenhouse effect and their future depletion, there is a constant search for environmentally friendly feedstock alternatives. Biomass residues constitute an interesting replacement for fossil resources because of their zero net CO₂ emissions. One of the main routes to convert biomass into energy and chemicals is pyrolysis. In this work, conventional pyrolysis of different biomass residues highly available such as almond shells, hemp hurds, olive stones, and Kraft lignin, was studied. In a typical experiment, the biomass was crushed and loaded into a fixed bed reactor under continuous nitrogen flow. The influence of temperature (400-800 ºC) and heating rate (10 and 20 ºC/min) on the pyrolysis yield and composition of the different fractions has been studied. In every case, the mass yields revealed that the solid fraction decreased with temperature, while liquid and gas fractions increased due to depolymerization and cracking reactions at high temperatures. The composition of every pyrolysis fraction was studied in detail. The results showed that the composition of the gas fraction was mainly CO, CO₂ when working at low temperatures, and mostly CH₄ and H₂at high temperatures. The solid fraction developed an incipient microporosity, with narrow micropore volume of 0.21 cm³/g. Regarding the liquid fraction, pyrolysis of almond shell, hemp hurds, and olive stones led mainly to a high content in aliphatic acids and furans, due to the high volatile matter content of these biomass (>74 %wt.), and phenols to a lesser degree, which were formed due to the degradation of lignin at higher temperatures. However, when Kraft lignin was used as bio-oil precursor, the presence of phenols was very prominent, and aliphatic compounds were also detected in a lesser extent.

Keywords: Bio-oil, biomass, conventional pyrolysis, lignocellulosic

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Authors: Adilah Shariff, Nur Syairah Mohamad Aziz, Norsyahidah Md Saleh, Nur Syuhada Izzati Ruzali

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The first objective of this study is to investigate the suitability of coconut frond (CF) and coconut husk (CH) as feedstocks using a laboratory-scale slow pyrolysis experimental setup. The second objective is to investigate the effect of pyrolysis temperature on the biochar yield. The properties of CF and CH feedstocks were compared. The properties of the CF and CH feedstocks were investigated using proximate and elemental analysis, lignocellulosic determination, and also thermogravimetric analysis (TGA). The CF and CH feedstocks were pyrolysed at 300, 400, 500, 600 and 700 °C for 2 hours at 10 °C/min heating rate. The proximate analysis showed that CF feedstock has 89.96 mf wt% volatile matter, 4.67 mf wt% ash content and 5.37 mf wt% fixed carbon. The lignocelluloses analysis showed that CF feedstock contained 21.46% lignin, 39.05% cellulose and 22.49% hemicelluloses. The CH feedstock contained 84.13 mf wt% volatile matter, 0.33 mf wt% ash content, 15.54 mf wt% fixed carbon, 28.22% lignin, 33.61% cellulose and 22.03% hemicelluloses. Carbon and oxygen are the major component of the CF and CH feedstock compositions. Both of CF and CH feedstocks contained very low percentage of sulfur, 0.77% and 0.33%, respectively. TGA analysis indicated that coconut wastes are easily degraded. It may be due to their high volatile content. Between the temperature ranges of 300 and 800 °C, the TGA curves showed that the weight percentage of CF feedstock is lower than CH feedstock by 0.62%-5.88%. From the D TGA curves, most of the weight loss occurred between 210 and 400 °C for both feedstocks. The maximum weight loss for both CF and CH are 0.0074 wt%/min and 0.0061 wt%/min, respectively, which occurred at 324.5 °C. The yield percentage of both CF and CH biochars decreased significantly as the pyrolysis temperature was increased. For CF biochar, the yield decreased from 49.40 wt% to 28.12 wt% as the temperature increased from 300 to 700 °C. The yield for CH biochars also decreased from 52.18 wt% to 28.72 wt%. The findings of this study indicated that both CF and CH are suitable feedstock for slow pyrolysis of biochar.

Keywords: biochar, biomass, coconut wastes, slow pyrolysis

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Authors: Julius Ilawe Osayi, Peter Osifo

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Solid waste disposal, such as used tires is a global challenge as well as energy crisis due to rising energy demand amidst price uncertainty and depleting fossil fuel reserves. Therefore, the effectiveness of pyrolysis as a disposal method that can transform used tires into liquid fuel and other end-products has made the process attractive to researchers. Although used tires have been converted to liquid fuel using pyrolysis, there is the need to improve on the liquid fuel properties. Hence, this paper reports the investigation of zeolite NaY synthesized from kaolin, a locally abundant soil material in the Benin metropolis as a suitable catalyst and its effect on the properties of pyrolytic oil produced from used tires. The pyrolysis process was conducted for a range of 1 to 10 wt.% of catalyst concentration to used tire at a temperature of 600 oC, a heating rate of 15oC/min and particle size of 6mm. Although no significant increase in pyrolytic oil yield was observed compared to the previously investigated non-catalytic pyrolysis of a used tire. However, the Fourier transform infrared (FTIR), Nuclear Magnetic Resonance (NMR); and Gas chromatography-mass spectrometry (GC-MS) characterization results revealed the pyrolytic oil to possess an improved physicochemical and fuel properties alongside valuable industrial chemical species. This confirms the possibility of transforming kaolin into a catalyst suitable for improved fuel properties of the liquid fraction obtainable from thermal cracking of hydrocarbon materials.

Keywords: catalytic pyrolysis, fossil fuel, kaolin, pyrolytic oil, used tyres, Zeolite NaY

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Authors: Said Sair, Hanane Ait Ousaleh, Ilyas Belghazi, Othmane Amadine

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Plastic waste has become a major environmental issue, driving the need for innovative solutions to convert it into valuable resources. This study explores the catalytic pyrolysis of plastic waste to produce hydrogen, using zeolite catalysts as a key component in the process. Various zeolites, including types X, A, and P, are synthesized and characterized through X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) surface area analysis, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). These techniques are employed to assess the structural and chemical properties of the catalysts. Catalytic pyrolysis experiments are performed under different conditions, including variations in temperature, catalyst loading, and reaction time, to optimize hydrogen production. The results demonstrate that the choice of zeolite catalyst significantly impacts plastic waste conversion efficiency into hydrogen. This research contributes to advancing circular economy principles by providing an effective method for plastic waste management and clean energy production, promoting environmental sustainability.

Keywords: hydrogen production, plastic waste, zeolite catalysts, catalytic pyrolysis, circular economy, sustainable energy

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Authors: Qian Li, Zhaoping Zhong

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Sewage sludge, a typical solid waste, has inevitably been produced in enormous quantities in China. Still worse, the amount of sewage sludge produced has been increasing due to rapid economic development and urbanization. Compared to the conventional method to treat sewage sludge, pyrolysis has been considered an economic and ecological technology because it can significantly reduce the sludge volume, completely kill pathogens, and produce valuable solid, gas, and liquid products. However, the large-scale utilization of sludge biochar has been limited due to the considerable risk posed by heavy metals in the sludge. Heavy metals enriched in pyrolytic biochar could be divided into exchangeable, reducible, oxidizable, and residual forms. The residual form of heavy metals is the most stable and cannot be used by organisms. Kaolin and zeolite are environmentally friendly inorganic minerals with a high surface area and heat resistance characteristics. So, they exhibit the enormous potential to immobilize heavy metals. In order to reduce the risk of leaching heavy metals in the pyrolysis biochar, this study pyrolyzed sewage sludge mixed with kaolin/zeolite in a small rotary kiln. The influences of additives and pyrolysis temperature on the leaching concentration and morphological transformation of heavy metals in pyrolysis biochar were investigated. The potential mechanism of stabilizing heavy metals in the co-pyrolysis of sludge blended with kaolin/zeolite was explained by scanning electron microscopy, X-ray diffraction, and specific surface area and porosity analysis. The European Community Bureau of Reference sequential extraction procedure has been applied to analyze the forms of heavy metals in sludge and pyrolysis biochar. All the concentrations of heavy metals were examined by flame atomic absorption spectrophotometry. Compared with the proportions of heavy metals associated with the F4 fraction in pyrolytic carbon prepared without additional agents, those in carbon obtained by co-pyrolysis of sludge and kaolin/zeolite increased. Increasing the additive dosage could improve the proportions of the stable fraction of various heavy metals in biochar. Kaolin exhibited a better effect on stabilizing heavy metals than zeolite. Aluminosilicate additives with excellent adsorption performance could capture more released heavy metals during sludge pyrolysis. Then heavy metal ions would react with the oxygen ions of additives to form silicate and aluminate, causing the conversion of heavy metals from unstable fractions (sulfate, chloride, etc.) to stable fractions (silicate, aluminate, etc.). This study reveals that the efficiency of stabilizing heavy metals depends on the formation of stable mineral compounds containing heavy metals in pyrolysis biochar.

Keywords: co-pyrolysis, heavy metals, immobilization mechanism, sewage sludge

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Authors: Bourfaa Fouzia, Meryem Lamri Zeggar, Adjimi Amel, Mohammed Salah Aida, Nadir Attaf

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Semiconductor photocatalysts such as ZnO has attracted much attention in recent years due to their various applications for the degradation of organic pollutants in water, air and in dye sensitized photovoltaic solar cell. In the present work, ZnO thin films were prepared by ultrasonic spray pyrolysis by using different precursors namely: Acetate, chloride and zinc nitrate in order to investigate their influence on ZnO photocatalytic activity. The films crystalline structure was studied by mean of X-ray diffraction measurements (XRD) and the films surface morphology by Scanning Electron Microscopy (SEM). The films optical properties were studied by mean of UV–visible spectroscopy. The prepared films were tested for the degradation of the red reactive dye largely used in textile industry. As a result, we found that the zinc nitrate is the best precursor to prepare ZnO thin films suitable for a good photocatalytic activity.

Keywords: precursor, thins films, spray pyrolysis, zinc oxide

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Authors: Shyh-Ming Chern, Wei-Ling Lin

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Lignin is a major constituent of woody biomass, and exists abundantly in nature. It is the major byproducts from the paper industry and bioethanol production processes. The byproducts are mainly used for low-valued applications. Instead, lignin can be converted into higher-valued gaseous fuel, thereby helping to curtail the ever-growing price of oil and to slow down the trend of global warming. Although biochemical treatment is capable of converting cellulose into liquid ethanol fuel, it cannot be applied to the conversion of lignin. Alternatively, it is possible to convert lignin into gaseous fuel thermochemically. In the present work, trans-4-hydroxycinnamic acid, a model compound for lignin, which closely resembles the basic building blocks of lignin, is gasified in an autoclave with ethanol at elevated temperatures and pressures, that are above the critical point of ethanol. Ethanol, instead of water, is chosen, because ethanol dissolves trans-4-hydroxycinnamic acid easily and helps to convert it into lighter gaseous species relatively well. The major operating parameters for the gasification reaction include temperature (673-873 K), reaction pressure (5-25 MPa) and feed concentration (0.05-0.3 M). Generally, more than 80% of the reactant, including trans-4-hydroxycinnamic acid and ethanol, were converted into gaseous products at an operating condition of 873 K and 5 MPa.

Keywords: ethanol, gasification, lignin, supercritical

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Authors: Martin Lisý, Marek Baláš, Michal Špiláček, Zdeněk Skála

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This paper deals with the issue of biomass and sorted municipal waste gasification and cogeneration using hot air turbo set. It brings description of designed pilot plant with electrical output 80 kWe. The generated gas is burned in secondary combustion chamber located beyond the gas generator. Flue gas flows through the heat exchanger where the compressed air is heated and consequently brought to a micro turbine. Except description, this paper brings our basic experiences from operating of pilot plant (operating parameters, contributions, problems during operating, etc.). The principal advantage of the given cycle is the fact that there is no contact between the generated gas and the turbine. So there is no need for costly and complicated gas cleaning which is the main source of operating problems in direct use in combustion engines because the content of impurities in the gas causes operation problems to the units due to clogging and tarring of working surfaces of engines and turbines, which may lead as far as serious damage to the equipment under operation. Another merit is the compact container package making installation of the facility easier or making it relatively more mobile. We imagine, this solution of cogeneration from biomass or waste can be suitable for small industrial or communal applications, for low output cogeneration.

Keywords: biomass, combustion, gasification, microcogeneration

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Authors: Martin Lisý, Marek Baláš, Michal Špiláček, Zdeněk Skála

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This paper deals with the issue of biomass and sorted municipal waste gasification and cogeneration using hot-air turbo-set. It brings description of designed pilot plant with electrical output 80 kWe. The generated gas is burned in secondary combustion chamber located beyond the gas generator. Flue gas flows through the heat exchanger where the compressed air is heated and consequently brought to a micro turbine. Except description, this paper brings our basic experiences from operating of pilot plant (operating parameters, contributions, problems during operating, etc.). The principal advantage of the given cycle is the fact that there is no contact between the generated gas and the turbine. So there is no need for costly and complicated gas cleaning which is the main source of operating problems in direct use in combustion engines because the content of impurities in the gas causes operation problems to the units due to clogging and tarring of working surfaces of engines and turbines, which may lead as far as serious damage to the equipment under operation. Another merit is the compact container package making installation of the facility easier or making it relatively more mobile. We imagine, this solution of cogeneration from biomass or waste can be suitable for small industrial or communal applications, for low output cogeneration.

Keywords: biomass, combustion, gasification, microcogeneration

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Authors: Mohammad Javad Afroughi, Farjad Falahati, Larry W. Kostiuk, Jason S. Olfert

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This study investigates the physical characteristics of nanoparticles generated during pyrolysis of methane in hot products of a premixed propane-air flame. An inverted burner is designed to provide a laminar premixed propane-air flame (35 SLPM) then introduce methane co-flow to be pyrolyzed within a closed cylindrical chamber (20 cm in diameter and 68 cm in length). The formed products are discharged through an exhaust with a sampling branch to measure emission characteristics. Carbon particles are sampled with a preheated nitrogen dilution system, and the size distribution of particles formed by pyrolysis is measured by a scanning mobility particle sizer (SMPS). Dilution ratio is calculated using simultaneously measured CO2 concentrations in the exhaust products and diluted samples. Results show that particle size distribution (PSD) is strongly affected by dilution ratio and preheating temperature. PSD becomes unstable at high dilution ratios (typically above 700 times) and/or low preheating temperatures (below 40° C). At a suitable dilution ratio of 55 and preheating temperature up to 70° C, the median diameter of PSD increases from 20 to 220 nm following the introduction of 0.5 SLPM of methane to the propane-air premixed flame. Furthermore, with pyrolysis of methane, total particle number concentration and estimated total mass concentration of particles in the size range of 14 to 700 nm, increase from 1.12 to 3.90 *107 cm-3 and from 0.11 to 154 µg L-1, respectively.

Keywords: laminar premixed flame, methane pyrolysis, nanoparticle physical characteristics, particle mass concentration, particle number concentration, particle size distribution (PSD)

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Authors: Jamshid Hussain, Kuen Song Lin

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Over one thousand tons of pig hair biowaste (PHB) are produced yearly in Taiwan. The improper disposal of PHB can have a negative impact on the environment, consequently contributing to the spread of diseases. The treatment of PHB has become a major environmental and economic challenge. Innovative treatments must be developed because of the heavy metal and sulfur content of PHB. Like most organic materials, PHB is composed of many organic volatiles that contain large amounts of hydrogen. Hydrogen gas can be effectively produced by the catalytic gasification of PHB using a laboratory-scale fixed-bed gasifier, employing 15 wt% NiO/Al₂O₃ catalyst at 753–913 K. The derived kinetic parameters were obtained and refined using simulation calculations. FE–SEM microphotograph showed that NiO/Al₂O₃ catalyst particles are Spherical or irregularly shaped with diameters of 10–20 nm. HR–TEM represented that the fresh Ni particles were evenly dispersed and uniform in the microstructure of Al₂O₃ support. The sizes of the NiO nanoparticles were vital in determining catalyst activity. As displayed in the pre-edge XANES spectra of the NiO/Al₂O₃ catalysts, it exhibited a non-intensive absorbance nature for the 1s to 3d transition, which is prohibited by the selection rule for an ideal octahedral symmetry. Similarly, the populace of Ni(II) and Ni(0) onto Al₂O₃ supports are proportional to the strength of the 1s to 4pxy transition, respectively. The weak shoulder at 8329–8334 eV and a strong character at 8345–8353 eV were ascribed to the 1s to 4pxy shift, which suggested the presence of NiO types onto Al₂O₃ support in PHB catalytic gasification. As determined by the XANES analyses, Ni(II)→Ni(0) reduction was mostly observed. The oxidation of PHB onto the NiO/Al₂O₃ surface may have resulted in Ni(0) and the formation of tar during the gasification process. The EXAFS spectra revealed that the Ni atoms with Ni–Ni/Ni–O bonds were found. The Ni–O bonding proved that the produced syngas were unable to reduce NiO to Ni(0) completely. The weakness of the Ni–Ni bonds may have been caused by the highly dispersed Ni in the Al₂O₃ support. The central Ni atoms have Ni–O (2.01 Å) and Ni–Ni (2.34 Å) bond distances in the fresh NiO/Al₂O₃ catalyst. The PHB was converted into hydrogen-rich syngas (CO + H₂, >89.8% dry basis). When PHB (250 kg h−1) was catalytically gasified at 753–913 K, syngas was produced at approximately 5.45 × 105 kcal h−1 of heat recovery with 76.5%–83.5% cold gas efficiency. The simulation of the pilot-scale PHB catalytic gasification demonstrated that the system could provide hydrogen (purity > 99.99%) and generate electricity for an internal combustion engine of 100 kW and a proton exchange membrane fuel cell (PEMFC) of 175 kW. A projected payback for a PHB catalytic gasification plant with a capacity of 10- or 20-TPD (ton per day) was around 3.2 or 2.5 years, respectively.

Keywords: pig hair biowaste, catalytic gasification, hydrogen production, PEMFC, resource recovery

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Authors: P. A. Broodryk, A. F. Van Der Merwe, H. W. J. P. Neomagus

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The production of the clear liquid fertilizer ammonium polyphosphate (APP) is best achieved by the pyrolysis of urea phosphate, as it produces a product that is free from any of the impurities present in the raw phosphoric acid it was made from. This is a multiphase, multi-step reaction that produces carbon dioxide and ammonia as gasses and ammonium polyphosphate as liquid products. The polyphosphate chain length affects the solubility and thus the applicability of the product as liquid fertiliser, thus proper control of the reaction conditions is thus required for the use of this reaction in the production of fertilisers. This study investigates the reaction kinetics of the aforementioned reaction, describing a mathematical model for the kinetics of the reaction along with the accompanying rate constants. The reaction is initially exothermic, producing only carbon dioxide as a gas product and ammonium diphosphate, at higher temperatures the reaction becomes endothermic, producing ammonia gas as an additional by-product and longer chain polyphosphates, which when condensed too far becomes highly water insoluble. The aim of this study was to (i) characterise the pyrolysis reaction of urea phosphate by determining the mechanisms and the associated kinetic constants, and (ii) to determine the optimum conditions for ammonium diphosphate production. A qualitative investigation was also done to find the rate of hydrolysis of APP as this provides an estimate of the shelf life of an APP clear liquid fertiliser solution.

Keywords: ammonium polyphosphate, kinetics, pyrolysis, urea phosphate

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. In this respect, biofuels are measured as a vital nominee for national energy security and energy sustainability. Sewage sludge (SS), as an alternative source of renewable energy with a complex composition, is a major waste generated during wastewater treatment. Stricter legislation is continuously refining the requirements for the level of removal of various pollutants in treated water, causing continuous growth of sludge production, which has become a global challenge. In general, there are two main procedures for dealing with SS: incineration and landfill. However, there are a variety of limitations in these options (e.g., production of greenhouse gases and restrictive environmental regulations) in regard to negative social and economic impacts. Pyrolysis is a feasible and cost-effective technology that can simultaneously tackle boundaries concerning the current disposal routes while retrieving bioenergy. Pyrolysis of SS has drawn vigorous interest in research due to the ability of high mass yield of pyrolytic liquid production. Nonetheless, the presence of high molecular weight hydrocarbons and oxygenated- and nitrogenated compounds poses a considerable challenge. In this context, catalytic pyrolysis is another attainable route in order to upgrade the bio-oil quality. Among different catalysts (i.e., zeolites) studied for sewage sludge pyrolysis, activated chars are eco-friendly and low-cost alternatives. The beneficial features comprise comparatively large surface area, long-term stability, and enriched surface functional groups. In light of these premises, this research attempts to investigate the catalytic pyrolysis of sewage sludge with a high-performance sludge-based activated char in contrast to HZSM5 from a theoretical and experimental point of view.

Keywords: catalytic pyrolysis, sewage sludge, char, HZSM5, bio-oil.

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Authors: M. A. Hannan, N. Matthias Neisius

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Organophosphorus compound diethyloxymethyl-9-oxa-10-phosphaphenanthrene-10-oxide (DOPAC) was applied on cotton cellulose to impart eco-friendly flame retardant property to it. Here acetal linkage was introduced rather than conventionally used ester linkage to rescue from the undurability problem of flame retardant compound. Some acidic catalysts, sodium dihydrogen phosphate (NaH2PO4), ammonium dihydrogen phosphate (NH4H2PO4) and phosphoric acid (H3PO4) were successfully used to form acetal linkage between the base material and flame retardant compound. Inspiring limiting oxygen index (LOI) value of 22.4 was found after exclusive washing treatment. A good outcome of total heat of combustion (THC) 6.05 KJ/g was found possible during pyrolysis combustion flow calorimetry (PCFC) test of the treated sample. Low temperature dehydration with sufficient amount of char residue (14.89%) was experienced in case of treated sample. In addition, the temperature of peak heat release rate (TPHRR) 343.061°C supported the expected low temperature pyrolysis in condensed phase mechanism. With the consequence of pyrolysis effects, thermogravimetric analysis (TGA) also reported inspiring weight retention% of the treated samples.

Keywords: acetal linkage, char residue, cotton cellulose, flame retardant, loi, low temperature pyrolysis, organophosphorus, THC, THRR

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Authors: Muhammed Ertuğrul Çeloğlu, Mehmet Yılmaz

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In this study, apricot seed shell, walnut shell, and sawdust were chosen as biomass sources. The materials were sorted by using a sieve No. 50 and the sieved materials were subjected to pyrolysis process at 400 °C, resulting in three different biochar products. The resulting biochar products were added to the bitumen at three different rates (5%, 10% and 15%), producing modified bitumen. Penetration, softening point, rotation viscometer and dynamic shear rheometer (DSR) tests were conducted on modified binders. Thus the modified bitumen, which was obtained by using additives at 3 different rates obtained from biochar produced at 400 °C temperatures of 3 different biomass sources were compared and the effects of pyrolysis temperature and additive rates were evaluated. As a result of the conducted tests, it was determined that the rheology of the pure bitumen improved significantly as a result of the modification of the bitumen with the biochar. Additionally, with biochar additive, it was determined that the rutting parameter values obtained from softening point, viscometer and DSR tests were increased while the values in terms of penetration and phase angle decreased. It was also observed that the most effective biomass is sawdust while the least effective was ground apricot seed shell.

Keywords: rheology, biomass, pyrolysis, biochar

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Authors: Anabel Fernandez, Leandro Rodriguez-Ortiz, Rosa RodríGuez

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Due to the negative impact of fossil fuels, renewable energies are promising sources to limit global temperature rise and damage to the environment. Also, the development of technology is focused on obtaining energetic products from renewable sources. In this study, a thermodynamic model including Exergy balance and a subsequent Life Cycle Assessment (LCA) were carried out for four subsystems of the integrated gasification-combustion of pinewood. Results of exergy analysis and LCA showed the process feasibility in terms of exergy efficiency and global energy efficiency of the life cycle (GEELC). Moreover, the energy return on investment (EROI) index was calculated. The global exergy efficiency resulted in 67 %. For pretreatment, reaction, cleaning, and electric generation subsystems, the results were 85, 59, 87, and 29 %, respectively. Results of LCA indicated that the emissions from the electric generation caused the most damage to the atmosphere, water, and soil. GEELC resulted in 31.09 % for the global process. This result suggested the environmental feasibility of an integrated gasification-combustion system. EROI resulted in 3.15, which determinates the sustainability of the process.

Keywords: exergy analysis, life cycle assessment (LCA), renewability, sustainability

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Authors: Seada Hussen Adem, Frie Ayalew Yimam

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Due to its high biomass output and potential to produce renewable energy, water hyacinth, a rapidly expanding aquatic weed, has gained recognition as a prospective bioenergy feedstock. Through a variety of conversion processes, such as anaerobic digestion, combustion, and gasification, this study suggests using water hyacinth to generate energy. The suggested strategy helps to reduce the annoyance brought on by the excessive growth of water hyacinth in Tana water bodies in addition to offering an alternate source of energy. The study emphasizes the value of environmentally friendly methods for managing Tana water resources as well as the potential of water hyacinth as a source of bioenergy.

Keywords: anaerobic digestion, bioenergy, combustion, gasification, water hyacinth

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Authors: Binod Shrestha, Sandrine Hoppe, Thierry Ghislain, Phillipe Marchal, Nicolas Brosse, Anthony Dufour

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The thermochemical conversion of lignin has received an increasing interest in the frame of different biorefinery concepts for the production of chemicals or energy. It is needed to better understand the physical and chemical conversion of lignin for feeder and reactor designs. In-situ rheology reveals the viscoelastic behaviour of lignin upon thermal conversion. The softening, re-solidification (char formation), swelling and shrinking behaviours are quantified during pyrolysis in real-time [1]. The in-situ rheology of an alkali lignin (Protobind 1000) was conducted in high torque controlled strain rheometer from 35°C to 400°C with a heating rate of 5°C.min-1. The swelling, through glass phase transition overlapped with depolymerization, and solidification (crosslinking and “char” formation) are two main phenomena observed during lignin pyrolysis. The onset of temperatures for softening and solidification for this lignin has been found to be 141°C and 248°C respectively. An ex-situ characterization of lignin/char residues obtained at different temperatures after quenching in the rheometer gives a clear understanding of the pathway of lignin degradation. The lignin residues were sampled from the mid-point temperatures of the softening range and solidification range to study the chemical transformations undergoing. Elemental analysis, FTIR and solid state NMR were conducted after quenching the solid residues (lignin/char). The quenched solid was also extracted by suitable solvent and followed by acetylation and GPC-UV analysis. The combination of 13C NMR and GPC-UV reveals the depolymerization followed by crosslinking of lignin/char. NMR and FTIR provide the evolution of functional moieties upon temperature. Physical and chemical mechanisms occurring during lignin pyrolysis are accounted in this study. Thanks to all these complementary methods.

Keywords: pyrolysis, bio-chemicals, valorization, mechanism, softening, solidification, cross linking, rheology, spectroscopic methods

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Authors: HyeSuk Ri, HyonChol Kim, NamChol Yu

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The FTO thin films were deposited on 15 cm × 15 cm glass substrates by ultrasonic spray pyrolysis, and the influence of process parameters on the film properties was investigated. This paper is the first report on the design of a uniform nozzle and simulating the carrier gas flow characteristics in an ultrasonic spray pyrolysis process. The uniformity of FTO films was evaluated by surface resistivity. The structure, surface morphology and optical properties of FTO films were investigated using scanning electron microscopy, X-ray diffraction, and UV-Vis spectroscopy. The process conditions for film preparation were SnCl₄ concentration of 1.34 mol, NH₄F concentration of 0.08 mol, temperature of 500 °C, deposition time of 15 min, carrier gas flow rate of 3 m/s, distance between nozzle and substrate of 0.7 cm. The transmittance of the fabricated FTO films was 80%, the surface resistance showed a uniform behavior at 14-15Ω/cm² and the X-ray analysis showed a high orientation of SnO₂ crystals in the 200-plane. SEM analysis showed that the crystallite size was constant.

Keywords: nozzle design, FTO film, simulation, ultrasonic spray pyrolysis

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Authors: Shyh-Ming Chern, Kai-Ting Hsieh

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Organic solvents find various applications in many industrial sectors and laboratories as dilution solvents, dispersion solvents, cleaners and even lubricants. Millions of tons of Spent Organic Solvents (SOS) are generated each year worldwide, prompting the need for more efficient, cleaner and safer methods for the treatment and resource recovery of SOS. As a result, acetone, selected as a model compound for SOS, was gasified in supercritical water to assess the feasibility of resource recovery of SOS by means of supercritical water processes. Experiments were conducted with an autoclave reactor. Gaseous product is mainly consists of H2, CO, CO2 and CH4. The effects of three major operating parameters, the reaction temperature, from 673 to 773K, the dosage of oxidizing agent, from 0.3 to 0.5 stoichiometric oxygen, and the concentration of acetone in the feed, 0.1 and 0.2M, on the product gas composition, yield and heating value were evaluated with the water density fixed at about 0.188g/ml.

Keywords: acetone, gasification, SCW, supercritical water

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Authors: Ibrahim Hakeem

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Biosolids are stabilised sewage sludge produced from wastewater treatment processes. Biosolids contain valuable plant nutrient which facilitates their beneficial reuse in agricultural land. However, the increasing levels of legacy and emerging contaminants such as heavy metals (HMs), PFAS, microplastics, pharmaceuticals, microbial pathogens etc., are restraining the direct land application of biosolids. Pyrolysis of biosolids can effectively degrade microbial and organic contaminants; however, HMs remain a persistent problem with biosolids and their pyrolysis-derived biochar. In this work, we demonstrated the integrated processing of biosolids involving the acid pre-treatment for HMs removal and selective reduction of ash-forming elements followed by the bench-scale pyrolysis of the treated biosolids to produce quality biochar and bio-oil enriched with valuable platform chemicals. The pre-treatment of biosolids using 3% v/v H₂SO₄ at room conditions for 30 min reduced the ash content from 30 wt% in raw biosolids to 15 wt% in the treated sample while removing about 80% of limiting HMs without degrading the organic matter. The preservation of nutrients and reduction of HMs concentration and mobility via the developed hydrometallurgical process improved the grade of the treated biosolids for beneficial land reuse. The co-removal of ash-forming elements from biosolids positively enhanced the fluidised bed pyrolysis of the acid-treated biosolids at 700 ℃. Organic matter devolatilisation was improved by 40%, and the produced biochar had higher surface area (107 m²/g), heating value (15 MJ/kg), fixed carbon (35 wt%), organic carbon retention (66% dry-ash free) compared to the raw biosolids biochar with surface area (56 m²/g), heating value (9 MJ/kg), fixed carbon (20 wt%) and organic carbon retention (50%). Pre-treatment also improved microporous structure development of the biochar and substantially decreased the HMs concentration and bioavailability by at least 50% relative to the raw biosolids biochar. The integrated process is a viable approach to enhancing value recovery from biosolids.

Keywords: biosolids, pyrolysis, biochar, heavy metals

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Authors: Hamad Almohamadi, Abdulrahman AlKassem, Majed Alamoudi

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Dumping Aluminum (Al) waste into landfills causes several health and environmental problems. The pyrolysis process could treat Al waste to produce AlCl₃ and H₂. Using the Aspen Plus software, a techno-economic and feasibility assessment has been performed for Al waste pyrolysis. The Aspen Plus simulation was employed to estimate the plant's mass and energy balance, which was assumed to process 100 dry metric tons of Al waste per day. This study looked at two cases of Al waste treatment. The first case produces 355 tons of AlCl₃ per day and 9 tons of H₂ per day without recycling. The conversion rate must be greater than 50% in case 1 to make a profit. In this case, the MSP for AlCl₃ is $768/ton. The plant would generate $25 million annually if the AlCl₃ were sold at $1000 per ton. In case 2 with recycling, the conversion has less impact on the plant's profitability than in case 1. Moreover, compared to case 1, the MSP of AlCl₃ has no significant influence on process profitability. In this scenario, if AlCl₃ were sold at $1000/ton, the process profit would be $58 million annually. Case 2 is better than case 1 because recycling Al generates a higher yield than converting it to AlCl₃ and H₂.

Keywords: aluminum waste, aspen plus, process modelling, fast pyrolysis, techno-economic assessment

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Authors: Yousaf Ayub

Abstract:

A co-gasification process, which involves the utilization of both biomass and plastic waste, has been developed to enable the production of blue and green hydrogen. To support this endeavor, an Aspen Plus simulation model has been meticulously created, and sustainability analysis is being conducted, focusing on economic viability, energy efficiency, advanced exergy considerations, and exergoeconomics evaluations. In terms of economic analysis, the process has demonstrated strong economic sustainability, as evidenced by an internal rate of return (IRR) of 8% at a process efficiency level of 70%. At present, the process has the potential to generate approximately 1100 kWh of electric power, with any excess electricity, beyond meeting the process requirements, capable of being harnessed for green hydrogen production via an alkaline electrolysis cell (AEC). This surplus electricity translates to a potential daily hydrogen production of around 200 kg. The exergy analysis of the model highlights that the gasifier component exhibits the lowest exergy efficiency, resulting in the highest energy losses, amounting to approximately 40%. Additionally, advanced exergy analysis findings pinpoint the gasifier as the primary source of exergy destruction, totaling around 9000 kW, with associated exergoeconomics costs amounting to 6500 $/h. Consequently, improving the gasifier's performance is a critical focal point for enhancing the overall sustainability of the process, encompassing energy, exergy, and economic considerations.

Keywords: blue hydrogen, green hydrogen, co-gasification, waste valorization, exergy analysis

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Authors: A. Ribeiro, N. Pacheco, M. Soares, N. Valério, L. Nascimento, A. Silva, C. Vilarinho, J. Carvalho

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Hydrogen will play a key role in changing the current global energy paradigm, associated with the high use of fossil fuels and the release of greenhouse gases. This work intended to identify and quantify the potential of Solid Recovered Fuels (SFR) existing in Portugal and project the cost of hydrogen, produced through its steam gasification in different scenarios, associated with the size or capacity of the plant and the existence of carbon capture and storage (CCS) systems. Therefore, it was performed a techno-economic analysis simulation using an ASPEN base model, the H2A Hydrogen Production Model Version 3.2018. Regarding the production of SRF, it was possible to verify the annual production of more than 200 thousand tons of SRF in Portugal in 2019. The results of the techno-economic analysis simulations showed that in the scenarios containing a high (200,000 tons/year) and medium (40,000 tons/year) amount of SFR, the cost of hydrogen production was competitive concerning the current prices of hydrogen. The results indicate that scenarios 1 and 2, which use 200,000 tons of SRF per year, have lower hydrogen production values, 1.22 USD/kg H2 and 1.63 USD/kg H2, respectively. The cost of producing hydrogen without carbon capture and storage (CCS) systems in an average amount of SFR (40,000 tons/year) was 1.70 USD/kg H2. In turn, scenarios 5 (without CCS) and 6 (with CCS), which use only 683 tons of SFR from urban sources, have the highest costs, 6.54 USD/kg H2 and 908.97 USD/kg H2, respectively. Therefore, it was possible to conclude that there is a huge potential for the use of SRF for the production of hydrogen through steam gasification in Portugal.

Keywords: gasification, hydrogen, solid recovered fuels, techno-economic analysis, waste-to-energy

Procedia PDF Downloads 125