The results of pyrolysis of pine chips and refuse derived fuel fractions are presented. The experiments were carried out in a pilot pyrolysis reactor. The feedstock was analyzed by an elemental analyzer and the X-ray fluorescence spectrometer to determine the elemental composition. To find out optimum conditions for pyrolysis and mass loss as a function of temperature the thermogravimetric analysis was applied. Gases from the thermogravimetric analysis were directed to the infrared spectrometer using gas-flow cuvette to online analysis of gas composition. Chemical composition of the produced gas was measured using gas chromatography with a thermal conductivity detector and a flame ionization detector. The product analysis also took into account the mass balance of individual products.
A mathematical model of waste tyre pyrolysis process is developed in this work. Tyre material decomposition based on a simplified reaction mechanism leads to main product lumps: noncondensable (gas), condensable (pyrolytic oil) and solid (char). The model takes into account kinetics of heat and mass transfer in the grain of the shredded rubber material as well as surrounding gas phase. The main reaction routes were modelled as the pseudo-first order reactions with a rate constant calculated from the Arrhenius type equation using literature values of activation energy determined for main tyre constituents based on TG/DTG measurements and tuned pre-exponential parameter values obtained by fitting theoretical predictions to the experimental results obtained in our laboratory reactor. The model was implemented within the CFD software (ANSYS Fluent). The results of numerical simulation of the pyrolysis process revealed non-uniformity of sample’s porosity and temperature. The simulation predictions were in satisfactory agreement with the experimentally measured mass loss of the tyre sample during pyrolysis process investigated in a laboratory reactor.
Anaerobic digestion residue represents a nutrient rich resource which, if applied back on land, can reduce the use of mineral fertilizers and improve soil fertility. However, dewatering and further thermal processing of digestate may be recommended in certain situations. Limited applicability of digestate as fertilizer may appear, especially in winter, during the vegetation period or in areas where advanced eutrophication of arable land and water bodies is developing. The use of digestate may be also governed by different laws depending on whether it is treated as fertilizer, sewage sludge or waste. The aim of this paper is to present the effects of thermal treatment of solid fraction of digestate by drying followed by pyrolysis and gasification. Pyrolysis was carried out at the temperature of about 500°C. During this process the composition of flammable gases was checked and their calorific value was assessed. Then, a comparative analysis of energy parameters of the digestate and the carbonizate was performed. Gasification of digestate was carried out at the temperature of about 850°C with use of CO2 as the gasifi cation agent. Gasification produced gas with higher calorific value than pyrolysis, but carbonizate from pyrolysis had good properties to be used as a solid fuel
A one-dimensional transient mathematical model describing thermal and flow phenomena during coal coking in an oven chamber was studied in the paper. It also accounts for heat conduction in the ceramic oven wall when assuming a constant temperature at the heating channel side. The model was solved numerically using partly implicit methods for gas flow and heat transfer problems. The histories of temperature, gas evolution and internal pressure were presented and analysed. The theoretical predictions of temperature change in the centre plane of the coke oven were compared with industrialscale measurements. Both, the experimental data and obtained numerical results show that moisture content determines the coking process dynamics, lagging the temperature increase above the water steam evaporation temperature and in consequence the total coking time. The phenomenon of internal pressure generation in the context of overlapping effects of simultaneously occurring coal transitions - devolatilisation and coal permeability decrease under plastic stage - was also discussed.
The article is focused onthe energetical balance of a technical system for the conversion of crushed tyres by pyrolysis. Process temperatures were set in the range from 500 to 650°C. Mass input of the material was 30 kg per hour. The aim of the article is to answer the following questions as regards the individual products: Under which process conditions can the highest quality of the individual products related to energy be reached? How does the thermal efficiency of the system change in reaction to various conditions of the process?
On the basis of the experimental measurements and calculations, apart from other things, it was discovered that the pyrolysis liquid reaches the highest energetic value, i.e. 42.7 MJ.kg-1, out of all the individual products of the pyrolysis process. Generated pyrolysis gas disposes of the highest lower calorific value 37.1 MJ.kg-1 and the pyrolysis coke disposes of the maximum 30.9 MJ kg-1. From the energetic balance, the thermal efficiency of the experimental unit under the stated operational modes ranging from about 52 % to 56 % has been estimated. Individual findings are elaborated on detail in the article.
The aim of this work was to determine the influence of liming on the process of pyrolysis. Three samples of sludge from two wastewater treatment plants were selected for this study on pyrolysis: sludge without liming and limed sludge from the Central Wastewater Treatment Plant in Ostrava and sludge from the Wastewater Treatment Plant in Sviadnov. The samples had different content of calcite (CaCO3). The limed sludge contained 7% of CaCO3, sludge without liming 3.8% and sludge without liming from WWTP Sviadnov contained 0.5% of calcite. The results of laboratory pyrolysis proved that limed sludge released the maximum amount of carbon - 55.46 %, while sludge without liming from WWTP Sviadnov released only 48.92%. Calcite produces during its decomposition CaO and the product influences the pyrolysis process because it supports cracking of volatile organic compounds
This paper shows the possibility that the mineral coal existing in the mining basins of northern Spain have a high added value. This would facilitate its future use in different fields such as new materials, nanotechnology, energy use in situ, coal bed methane, enhanced coal bed methane and coalmine methane.
An analytical study of mineral coal samples is carried out. The samples come from two deposits located in coal basins of the Cantabrian Mountains. The duly prepared samples are subjected to an activation process. Within this transformation, different treatments are applied to different sub-samples. Some of the sub-samples suffer a previous demineralization by successive attacks with acids, followed by oxidation and pyrolysis. Finally, all of them are activated with CO2 and H2O(steam).
The carbonaceous products resulting from each treatment are characterised. The results show that all the pre-treatments used were positive for the textural development of the materials. Likewise, proper management of the processes and of the different operating variables allows the procurement of carbonaceous materials with a “tailor-made” structural development of the coal type. This material receives the name “activated” and can be employed in specific processes.
Results for microcrystalline cellulose pyrolysis are presented, which includes thermogravimetric measurements and kinetic analysis of experimental data. The effect of sample mass size and heating rate on estimated values of activation energy and pre-exponential factor is demonstrated and a simple modification of procedure is proposed that allows for the correct values of kinetic parameters regardless of the experimental conditions. The efficiency of the proposed method is confirmed for two endothermic chemical reactions. A method of nonlinear regression is used for calculation of kinetic parameters for a single or TG curve or several curves simultaneously.
This paper presents a systematic thermogravimetric (TG) study on the kinetics of end-of-life tyre (ELT) pyrolysis. In the experimental part of this work, TG results are compared for tyre samples of different mass and size. This shows that the conduction resistance in the milligram scale (up to ~100 mg) tyre sample can be neglected. A comparison of experimental results demonstrates that the characteristic maxima on the DTG curve (the first derivative of TG signal) shift towards higher temperatures for higher heating rates. This phenomenon is explained to have kinetic origin and it is not caused by the internal heat transfer resistance. In the modelling part of this work, the kinetic parameters of the Three-Component Simulation Model (TCSM) are calculated and compared to the literature values. Testing of the kinetic model is carried out using experiments with a varying heating rate. This shows the limitation of the simplified kinetic approach and the appropriate selection method of the kinetic parameters.
Sand samples with furan binder were prepared using Sand, Furfuryl Alcohol and Toluene Sulfonic Acid with ratio 100:0.85:0.30. To
identify and quantify gases releasing from furan binder various studies like FTIR, TGA and GC-MS were carried out. After analyzing our
materials using above mentioned characterizations the chemical formula of the Resin and Binder and amount of gases releasing from
composition were confirmed. After studying various reports on pyrolysis process of furan binder calculation of the % of various gases
emitting during pyrolysis process of furan was carried out. Sample of gas collected from mold was analyzed using GC-MS. Based on GCMS
measurement various gases emitting from furan sand mold were identified and their amount were calculate and compared with the
international standers of permissible gas emission limits in a foundry. The purpose of this paper is to assist foundries in pollution
prevention by devising clean technologies which maintain or improve the quality of ambient surrounding. This paper aimed at
minimization of pollution of air by using various techniques.
The aim of this work was to investigate the heat and mass transfer during thermal decomposition of a single solid fuel particle. The problem regards the pyrolysis process which occurs in the absence of oxygen in the first stage of fuel oxidation. Moreover, the mass transfer during heating of the solid fuels is the basic phenomenon in the pyrolysis-derived alternative fuels (gas, liquid and solid phase) and in the gasification process which is focused on the generation of syngas (gas phase) and char (solid phase). Numerical simulations concern pyrolysis process of a single solid particle which occurs as a consequence of the particle temperature increase. The research was aimed at an analysis of the influence of particle physical properties on the devolatilization process. In the mathematical modeling the fuel grain is treated as an ideal sphere which consists of porous material (solid and gaseous phase), so as to simplify the final form of the partial differential equations. Assumption that the physical properties change only in the radial direction, reduces the partial derivatives of the angular coordinates. This leads to obtaining the equations which are only the functions of the radial coordinate. The model consists of the mass, momentum and energy equations for porous spherical solid particle heated by the stream of hot gas. The mass source term was determined in the wide range of the temperature according to the experimental data. The devolatilization rate was defined by the Arrhenius formula. The results of numerical simulation show that the heating and devolatilization time strongly depend on the physical properties of fuel. Moreover, proposed model allows to determine the pyrolysis process direction, which is limited by the equilibrium state.
It is estimated that the amount of used car tires in the European Union in 2016 was established at the level of 3,515,000 Mg, which is undoubtedly a problem from the point of view of engineering and environmental protection. An alternative to storing this waste in landfills is their pyrolysis. As a result of thermal decomposition, calorific value products (oil and gas fraction) are obtained, as well as a solid residue, which due to its composition and properties can be processed into a high quality carbon sorbent. For this purpose, various methods of modification of the pyrolyzate are used, both involving physical and chemical activation. This article presents the characteristics of solid residue after the pyrolysis of rubber tires running at a temperature of about 400°C, which included an analysis of chemical composition (XRF and IR), mineralogical composition (XRD, SEM-EDS) and textural characteristics. Additionally, for the purpose of activation, the sample was treated with nitrogen at a temperature of 550°C. The mineralogical analysis showed that the dominant mineral component is carbon. In addition, the presence of quartz, calcite and sphalerite was observed. Analysis of the chemical composition suggests that due to the high carbon content (about 80% by mass) it is possible for a carbon sorbent from the analyzed waste to be obtained. However, previous preliminary studies did not allow a material constituting a substitute for activated carbon to be obtained, because the applied modification only slightly increased the BET specific surface area, which reached the value of approx. 85 m2/g. Based on the analysis of the pore size distribution of the 2 tested samples, it was found to be homogeneous/modal with a micro/mesoporous nature, while the shape of the hysteresis loop suggests the presence of “bottle shape” pores. Due to the relatively high content of zinc, the composition of waste (about 4% of mass), the possibility of recovery of this element should also be considered.
There is general agreement that primary pyrolysis products of end-of-life tyres should be valorised to improve the economics of pyrolysis. In this work, tyre pyrolysis char (TPC) is produced in a pyrolysis pilot plant designed and built at our home university. The produced TPC was upgraded to tyre-derived activated carbon (TDAC) by activation with CO2, and then characterised using stereological analysis (SA) and nitrogen adsorption at 77 K. SA showed that the grains of TPC and TDAC were quasi- spherical and slightly elongated with a 25% increase in the mean particle cross-section surface area for TDAC. The textural properties of TDAC demonstrated the BET and micropore surface areas of 259 and 70 m2/g, respectively. Micropore volume and micropore surface area were 5.8 and 6.7 times higher for TDAC than TPC at 2 nm, respectively. The n-hexane adsorption was investigated using experiments and modelling. Eight adsorption isotherms along with three error functions were tested to model the adsorption equilibrium. The optimum sets of isotherm parameters were chosen by comparing sum of the normalized errors. The analysis indicated that the Freundlich isotherm gave the best agreement with the equilibrium experiments. In relation to different activated carbons, the adsorption capacity of TDAC for n-hexane is about 16.2 times higher than that of the worst reference material and 4.3 times lower than that of the best reference material. In addition, stereological analysis showed that activation with CO2 did not change the grain’s shape factors. However, a 25% increase in the mean particle cross-section surface area for TDAC was observed.
This paper aims to show the effect of activation method of tyre pyrolysis char (TPC) on adsorption of bisphenol A (BPA) from aqueous solutions. The TPC was produced from end-of-life-tyres (ELT) feedstock in a pilot plant at 773 K. Activation was accomplished using two classical methods: physical activation withCO2 and chemical activation withKOH. The two produced adsorbents had pores ranging from micro- to macropores. Distinct differences in the BET surface areas and pore volumes between the adsorbents were displayed showing better performance of the chemically activated adsorbent for adsorption of BPA from water.
The results of the kinetic studies showed that the adsorption of BPA followed pseudo-second-order kinetic model. The Freundlich, Langmuir, Langmuir–Freundlich and Redlich–Peterson isotherm equations were used for description of the adsorption data. The Langmuir–Freundlich isotherm model best fits the experimental data for the BPA adsorption on both adsorbents. The Langmuir–Freundlich monolayer adsorption capacity, qmLF, obtained for the CO2-activated tyre pyrolysis char (AP-CO2) and KOH-activated tyre pyrolysis char (AP-KOH) were 0.473 and 0.969 mmol g��1, respectively.