Investigation on pyrolysis of Moroccan oil shale/plastic mixtures by thermogravimetric analysis

Thermal degradation processes for a series of mixtures of oil shale/plastic were investigated using thermogravimetric analysis (TGA) at four heating rates of 2, 10, 20 and 50 K min^− 1 from ambient temperature to 1273 K. High density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP) were selected as plastic samples. Based on the results obtained, three thermal stages were identified during the thermal degradation. The first is attributed to the drying of absorbed water; the second was dominated by the overlapping of organic matter and plastic pyrolysis, while the third was linked to the mineral matter pyrolysis, which occurred at much higher temperatures. Discrepancies between the experimental and calculated TG/DTG profiles were considered as a measurement of the extent of interactions occurring on co-pyrolysis. The maximum degradation temperatures of each component in the mixture were higher than those of the individual components; thus an increase in thermal stability was expected. In addition, a kinetic analysis was performed to fit thermogravimetric data. A reasonable fit to the experimental data was obtained for all materials and their mixtures.     

Thermogravimetric analysis and kinetics of coal/plastic blends during co-pyrolysis in nitrogen atmosphere

Investigations into the co-pyrolytic behaviours of different plastics (high density polyethylene, low density polyethylene and polypropylene), low volatile coal and their blends with the addition of the plastic of 5 wt.% have been conducted using a thermogravimetric analyzer. The results indicated that plastic was decomposed in the temperature range 438–521 °C, while the thermal degradation temperature of coal was 174–710 °C. The overlapping degradation temperature interval between coal and plastic was favorable for hydrogen transfer from plastic to coal. The difference of weight loss (?W) between experimental and theoretical ones, calculated as an algebraic sum of those from each separated component, was 2.0–2.7% at 550–650 °C. These experimental results indicated a synergistic effect during plastic and coal co-pyrolysis at the high temperature region. In addition, a kinetic analysis was performed to fit thermogavimetric data, the estimated kinetic parameters (activation energies and pre-exponential factors) for coal, plastic and their blends, were found to be in the range of 35.7–572.8 kJ/mol and 27–1.7 × 10³⁸ min^− 1, respectively.     

Thermogravimetric characteristics and kinetic of plastic and biomass blends co-pyrolysis

Co-pyrolytic behaviours of plastic/biomass mixtures were investigated using a thermogravimetric analyser under heating rate of 20 °C/min from room temperature to 650 °C. The biomass sample selected was Chinese pine wood sawdust, while high density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene were selected as plastic samples. Results obtained from this comprehensive investigation indicated that plastic was decomposed in the temperature range 438–521 °C, while the thermal degradation temperature of biomass is 292–480 °C. The difference of weight loss (ΔW) between experimental and theoretical ones, calculated as algebraic sums of those from each separated component, is about 6–12% at 530–650 °C. These experimental results indicate a significant synergistic effect during plastic and biomass co-pyrolysis at the high temperature region. In addition, a kinetic analysis was performed to fit thermogravimetric data, the global processes being considered as one to three consecutive first order reactions. A reasonable fit to the experimental data was obtained for all materials and their blends.     

Thermogravimetric characteristics and kinetic study of biomass co-pyrolysis with plastics

The pyrolysis of pure biomass, high density polyethylene (HDPE), polypropylene (PP) and polyethylene terephthalate (PET), plastic mixtures [HDPE+PP+PET (1: 1: 1)], and biomass/plastic mixture (9: 1, 3: 1, 1: 1, 1: 3 and 1: 9) were investigated by using a thermogravimetric analyzer under a heating rate at 10 °C/min from room temperature to 800 °C. Paper was selected as the biomass sample. Results obtained from this comprehensive investigation indicated that biomass was decomposed mainly in the temperature range of 290–420 °C, whereas thermal degradation temperature of plastic mixture is 390–550 °C. The percentage weight loss difference (W) between experimental and theoretical ones was calculated, which reached a significantly high value of (−)15 to (−)50% at around 450 °C in various blend materials. These thermogravimetric results indicate the presence of significant interaction and synergistic effect between biomass and plastic mixtures during their co-pyrolysis at the high temperature region. With increase in the amount of plastic mixture in blend material, the char production has diminished at final pyrolysis temperature range. Additionally, a kinetic analysis was performed to fit with TGA data, the entire pyrolysis processes being considered as one or two consecutive first order reactions.     

Thermal degradation of rice-bran with high density polyethylene: A kinetic study

Thermal degradation behavior of mixtures of rice bran (RB) and high density polyethylene (HDPE) was investigated by thermo-gravimetric analyses (TGA) under dynamic conditions in nitrogen atmosphere and was compared with that of individual materials. Experiments were carried out in the range of ambient temperature to 900 °C at two heating rates (5 and 20 °C per minute). Kinetic analysis indicated that activation energy for pyrolysis of RB, HDPE and those for RB-HDPE mixtures varied with rate of heating as well as with the three temperature ranges. This variation has been explained on the materials’ decomposition behavior. Maximum difference between experimental and theoretical mass loss (Δm) was 26% at 475 °C and 34% at 489 °C at the heating rates of 5 and 20 °C per minute, respectively. These maxima indicate stronger interactions at corresponding temperature between RB and HDPE during copyrolysis. Reduction in activation energy for pyrolysis, lower temperatures at which rate of decomposition is highest, and negligible quantity of the residue suggest a synergism between thermal degradation of RB and HDPE.     

Air and oxy-fuel combustion characteristics of biomass/lignite blends in TGA-FTIR

Pyrolysis and combustion behavior of indigenous lignite, olive residue and their 50/50 wt.% blend in air and oxy-fuel conditions were investigated by using thermogravimetric analyser (TGA) combined with Fourier-transform infrared (FTIR) spectrometer. Pyrolysis tests were carried out in nitrogen and carbon dioxide environments which are the main diluting gasses of air and oxy-fuel environment, respectively. Pyrolysis results of the parent fuels and the blend show that weight loss profiles are almost the same up to a temperature of 700 °C in these two environments, indicating that CO₂ behaves as an inert gas in this temperature range. However, further weight loss takes place in CO₂ atmosphere at higher temperatures due to CO₂-char gasification reaction which leads to significant increase in CO and COS formation as observed in FTIR evolution profiles. Comparison between experimental and theoretical pyrolysis profiles of the blend samples reveals that there is no synergy in both atmospheres. Combustion experiments were carried out in four different atmospheres; air, oxygen-enriched air environment (30% O2-70% N₂), oxy-fuel environment (21% O₂-79% CO₂) and oxygen-enriched oxy-fuel environment (30% O2-70% CO₂). Replacing N₂ in the combustion environment by CO₂ causes slight delay (lower maximum rate of weight loss and higher burnout temperature) in the combustion of all samples. However, this effect is found to be more significant for olive residue than lignite. Elevated oxygen levels shift combustion profiles to lower temperatures and increase the rate of weight loss. Combustion profiles of olive residue/lignite blends lie between those of individual fuels. Comparison between experimental and theoretical combustion profiles and characteristic temperatures of the blend samples indicates synergistic interactions between the parent fuels during co-combustion of olive residue and lignite.     

Continuous thermal degradation of pyrolytic oil in a bench scale CSTR reaction system

Continuous thermal degradation of two pyrolytic oils with low (LPO) and high boiling point distribution (HPO) was conducted in a constant stirrer tank reactor (CSTR) with bench scale. Raw pyrolytic oil as a reactant was obtained from the commercial rotary kiln pyrolysis plant for municipal plastic waste. The degradation experiment was conducted by temperature programming with 10 °C/min of heating rate up to 450 °C and then maintained with long lapse time at 450 °C. Liquid product was sampled at initial reaction time with different degradation temperatures up to 450 °C and then constant interval lapse time at 450 °C. The product characteristics over two pyrolytic oils were compared by using a continuous reaction system. As a reactant, heavy pyrolytic oil (HPO) showed higher boiling point distribution than that of diesel and also light pyrolytic oil (LPO) was mainly consisting of a mixture of gasoline and kerosene range components. In the continuous reaction, LPO showed higher yield of liquid product and lower residue than those of HPO. The characteristics of liquid products were influenced by the type of raw pyrolytic oil. Also, the result obtained under degradation temperature programming was described.     

Pyrolysis-gasification of plastics, mixed plastics and real-world plastic waste with and without Ni-Mg-Al catalyst

Polypropylene, polystyrene, high density polyethylene and their mixtures and real-world plastic waste were investigated for the production of hydrogen in a two-stage pyrolysis-gasification reactor. The experiments were carried out at gasification temperatures of 800 or 850 °C with or without a Ni-Mg-Al catalyst. The influence of plastic type on the product distribution and hydrogen production in relation to process conditions were investigated. The reacted Ni-Mg-Al catalysts were analyzed by temperature-programmed oxidation and scanning electron microscopy. The results showed that lower gas yield (11.2 wt.% related to the mass of plastic) was obtained for the non-catalytic non-steam pyrolysis-gasification of polystyrene at the gasification temperature of 800 °C, compared with the polypropylene (59.6 wt.%) and high density polyethylene (53.5 wt.%) and waste plastic (45.5 wt.%). In addition, the largest oil product was observed for the non-catalytic pyrolysis-gasification of polystyrene. The presence of the Ni-Mg-Al catalyst greatly improved the steam pyrolysis-gasification of plastics for hydrogen production. The steam catalytic pyrolysis-gasification of polystyrene presented the lowest hydrogen production of 0.155 and 0.196 (g H₂/g polystyrene) at the gasification temperatures of 800 and 850 °C, respectively. More coke was deposited on the catalyst for the pyrolysis-gasification of polypropylene and waste plastic compared with steam catalytic pyrolysis-gasification of polystyrene and high density polyethylene. Filamentous carbons were observed for the used Ni-Mg-Al catalysts from the pyrolysis-gasification of polypropylene, high density polyethylene, waste plastic and mixed plastics. However, the formation of filamentous carbons on the coked catalyst from the pyrolysis-gasification of polystyrene was low.     

Pyrolysis of waste-derived fuel mixtures containing PVC

This paper describes an experimental analysis of the pyrolysis of PVC and mixtures of PVC with wood (Finnish pine) and LDPE (low density polyethene) in nitrogen at 250-400 °C. The aim is to optimise the temperature range for producing low-chlorine or chlorine-free fuel in a dehydrochlorination reactor without pyrolysing any of the other combustible fractions. Results are presented for various process temperatures for PVC, PVC/wood and PVC/LDPE mixtures. It was found that the PVC tested is dehydrochlorinated at approximately 350 °C, and that secondary pyrolysis is suppressed when LDPE is present.     

Pyrolysis of polyolefins in high-boiling solvents

The pyrolysis of polyethylene and polypropylene in vacuum residue and coal-tar pitch solvents was studied in a batch reactor at atmospheric pressure in a temperature range of 380–420°C. Aliphatic hydrocarbons and C₅–C₃₂ normal olefins and isoolefins were the main pyrolysis products of the polyolefins and vacuum residue, which also underwent thermal degradation at these temperatures. The total conversion of a polypropylene-vacuum residue mixture into gaseous and distillate products was nearly additive; upon the pyrolysis of polypropylene in pitch and of polyethylene in vacuum residue and pitch, the yield of distillate products decreased and the paraffin/olefin ratio in these products increased. The observed regularities were explained by hydrogen transfer from the solvents to the intermediate radical products of the thermal decomposition of polymer chains. The reactions of the resulting of olefins with the solvents can also occur to a lesser degree. The greatest deviations from additivity were observed in the pyrolysis of polyethylene in the solvents used.     

Pyrolysis of synthetic polymers and plastic wastes. Kinetic study

Thermal decomposition of natural polystyrene, recycled plastics, low density polyethylene, acrylonitrile butadiene styrene, polyenterophthalate of ethylene, and polypropylene has been carried out. Both isothermal and dynamic experiments at different heating rates have been performed in a thermobalance with the objective of determining the kinetic parameters. Also, a first set of experiments, performed in a cylindrical stainless-steel atmospheric pressure reactor, was designed to evaluate the products of the pyrolysis process. The effects of N₂ flow rate (200–300 cm³ min^− 1), initial mass fed to the reactor (15–75 mg), temperature (415–490 °C), and heating rate (5–30 K min^− 1) were studied. By application of a first order kinetic model, the activation energy for every plastic has been determined. The values of activation energy in isothermic and dynamic regimen are the following: natural polystyrene: 136, and 168 to 286 kJ/mol. Recycled plastic: 250, and 150 to 290 kJ/mol. Low density polyethylene: 285, and 220 to 259 kJ/mol. Acrylonitrile butadiene styrene: 118, and 104 to 251 kJ/mol. Polyenterophthalate of ethylene: 161, and 117 to 255 kJ/mol. Polypropylene: 169, and 153 to 265 kJ/mol.     

Combustion properties of some power station biomass fuels

In this study, the combustion properties of three of the UK’s commonly imported biomass fuels for co-firing, which are palm kernel expellers, shea residue, and waste from olive oil production are examined. The fuels were characterised and their thermal decomposition properties were studied by thermogravimetric analysis (TGA). Additionally the products from their devolatilisation were identified by gas chromatography-mass spectrometry (py-GC-MS) analysis of the evolved vapours and tars from high heating rate pyrolysis tests. Finally, chars from the fuels were prepared, analysed, and combustion studies were conducted by TGA-MS to determine the conversion of char-nitrogen to different nitrogen-containing species. In general, the main constituents of their ash fractions were K, Si, Ca and Mg, resulting in high alkali indices, which predict a large tendency to fouling. The pyrolysis and combustion kinetic parameters, estimated from TGA studies of these fuels and their chars, are much lower than those reported in the literature for lignocellulosic biomass. It is suspected that there is oil/fat evaporation processes overlapping with the decomposition of their lignocellulosic fractions, which significantly affects the apparent kinetics. The pyrolysis conditions used promoted depletion of nitrogen in the char, resulting in approximately 79-91% of the fuel-N being released with the volatiles. In combustion of the char, NO_x and N₂ are the major nitrogen compounds detected. Another primary product, HCN, was detected from the combustion of some of the fuel chars, as well as C₂N₂.     

Co-pyrolysis of polymethyl methacrylate with brown coal and effect on monomer production

Pyrolysis capillary gas chromatography has been applied to the study of the co-pyrolysis of polymethyl methacrylate (PMMA) with Slovakian brown coal with the aim of finding pyrolysis conditions yielding a maximum amount of methyl methacrylate (MMA). Effects of pyrolysis temperature and PMMA-coal weight ratios were investigated. Capillary gas chromatography coupled with mass spectrometric detector (cGC-MS) was used for MMA identification. The highest yield of MMA in the pyrolysate was obtained at 750 °C. The optimal PMMA-coal weight ratio for maximum MMA production lies in the interval 0.5 mg PMMA and 0.6-0.8 mg brown coal with an MMA yield of 64%. Coal addition to the sample affects species recombination in gaseous phase, augments MMA production at higher temperatures and eliminates degradation products of PMMA and coal pyrolysis. Different conversion diagrams are characteristic for thermal degradation of single PMMA and in the mixture with coal. Detailed mechanism of synergetic effects arisen during co-pyrolysis are not yet known. It was also found that lower pyrolysis temperatures are more suitable to study degradation mechanism and kinetics while higher temperatures are more applicable for identification purposes. MMA decomposes completely at 900 °C.     

Volumetric properties of carbon dioxide + 2-butanol mixtures at 313.15 K

Volumetric properties were measured of carbon dioxide + 2-butanol mixtures at 313.15 K, using the vibrating tube Anton Paar DMA 512P density meter. In the present experiments, no analytical instrument was required. The saturated pressures were also measured of carbon dioxide + 2-butanol mixtures at 313.15 K by the synthetic method. The experimental data obtained were correlated with the density equation, Soave-Redlich-Kwong (SRK) equation of state, and the pseudocubic equation of state.     

Wood/plastic copyrolysis in an auger reactor: Chemical and physical analysis of the products

Previous studies observed that slow copyrolysis of wood and plastic in enclosed autoclaves produced an upgraded raw bio-oil with increased hydrogen content. We now demonstrate that fast simultaneous pyrolyses of 50:50, w/w, pine wood/waste plastics in a 2 kg/h lab scale auger-fed reactor at 1 atm, with a short vapor residence time, generates higher heating value upgraded bio-oils. Three plastics: polystyrene (PS), high density polyethylene (HDPE) and polypropylene (PP) were individually copyrolyzed with southern yellow pine wood at 525, 450 and 450 °C, respectively, to generate modified bio-oils upon condensation. These liquids exhibited higher carbon and hydrogen contents, significantly lower oxygen contents, higher heats of combustion and lower water contents, acid values and viscosities than pine bio-oil. The formation of cross-over wood/plastic reaction products was negligible in the oils. Simultaneous pyrolysis process design requires using a temperature at which the plastic’s thermal decomposition kinetics produce vapors rapidly enough to prevent vaporized plastic from condensing on wood chars and exiting the reactor.     

Hydrous pyrolysis of two kinds of low-rank coal for relatively long duration

Brown coal samples were treated with hot water in a stainless steel batch reactor at 623 K for 2-72 h. After this hot hydrous treatment, gas, oils, and residues were recovered. The resulting residues were chemically analyzed in detail to understand the reaction chemistry during hydrous pyrolysis. Oxygen functionalities were analyzed chemically with the titration method and carbon types in the residue were examined by solid-state ¹³C NMR measurement. Elemental analyses showed that the oxygen atoms in the residue decreased markedly up to 2 h while treatments longer than 48 h were also very effective in removing oxygen functionalities from brown coal. The detailed chemical analyses revealed that alcoholic hydroxyl and carboxyl groups were decomposed in the earlier stages of the treatment, and that ether bonds may be cleaved during the latter stages of the hot hydrous pyrolysis. Experiments using two kinds of brown coal gave very different results. A comparison of the chemical structure of these two coals revealed the origin of the difference; one of them has a greater amount of hydroaromatic moieties than the other, which act as a hydrogen source even during hydrous pyrolysis occurring at temperatures as low as 623 K.     

Two stages catalytic pyrolysis of olive oil waste

A study of the pyrolysis of a waste from the extraction of olive oil has been carried out. The work objective was to characterize the char, tar and gaseous phases generated in the process for their possible utilization in energy generation. On the other hand, the influence of a set of variables has been studied, including the efficacy of the dolomite as catalyst. Finally, as previous step to the design of industrial installations, a kinetic study of the process (catalyzed and uncatalyzed), based in the generation of the principal gases, has been carried out. In the uncatalyzed process only the influence of temperature (400–900 °C) was studied. In the catalytic process, the influence of temperature (500–800 °C) and mass of catalyst (0–100 g) was studied. Also, the dolomite effectiveness as catalyst was evaluated. For this motive, consecutive experiments, without reactivating dolomite, were carried out (0–6 runs), and the yields of solids, liquids and gases were determined. An increase in reaction temperature leads to a decrease in char and tar yield and to an increase in the gas phase yield. When the catalyst is present and when the mass of the same is increased, an important decrease in the tar yield and a high increase in the gas phase yield are produced. This increment in the yield of gases is very significant in the case of hydrogen. In addition, the catalyst is very stable. Your activity remains constant during six consecutive pyrolysis experiments, without need to carry out the reactivation of the same. In the kinetic study carried out, it has been considered that the gases are formed through parallel independent first-order reactions, with different activation energy. For uncatalyzed experiments, the experimental data, once adjusted to the model, provided activation energies of 77.8, 38.6, 70.5 and 16.9 kJ mol^− 1 and the Arrhenius pre-exponential factors of 210.1, 9.9, 775.3 and 0.43 min^− 1 for H₂, CO, CH₄, and CO₂, respectively. For catalyzed experiments (following the same sequence) the activation energies were 15.6, 16.5, 12.7 and 23.3 kJ mol^− 1 and the Arrhenius pre-exponential factors 3.8, 1.4, 4.3 and 3.5 min^− 1.     

Copyrolysis of oils/waxes of individual and mixed polyalkenes cracking products with petroleum fraction

Copyrolysis of 10 mass% solutions (oils/waxes from individual or mixed polymers with heavy naphtha) is a route for treatment of plastic waste. Linear low-density polyethylene (LLDPE), mixture of high-density polyethylene/low-density polyethylene/linear low-density polyethylene/polypropylene (HDPE/LDPE/LLDPE/PP = 1:1:1:1mass) and linear low-density polyethylene/low-density polyethylene/polypropylene/high-density polyethylene/polyvinyl chloride/polyethylene terepthalate/polystyrene (LLDPE/LDPE/PP/HDPE/PVC/PET/PS = 1:1:2:2:0.05:0.05:0.156 mass) were converted to oils/waxes, gases and solid residues by thermal decomposition in batch reactor at 450 °C. Oils/waxes were dissolved in virgin heavy naphtha to create the feedstock. The influence of residence time from 0.08 to 0.51 s at temperatures 780 °C and 820 °C on product distribution during the copyrolysis was studied. The yields obtained from gaseous and liquid products of solutions are compared to the yields obtained from virgin heavy naphtha. It was studied how addition of the oil/wax influences formation of C₂ and C₃ hydrocarbons (mainly ethene and propene) and aromatics in comparison to the virgin heavy naphtha. The ethene and propene yields from copyrolysis of solutions are comparable or higher than from virgin heavy naphtha. Copyrolysis of solution LLDPE/LDPE/PP/HDPE/PVC/PET/PS gives the maximum yields of propene from all studied oils/waxes. The result suggests that oils/waxes from polymers are suitable feedstocks for copyrolysis with virgin heavy naphtha.     

Recycling poly-(methyl methacrylate) by pyrolysis in a conical spouted bed reactor

The pyrolysis of poly-(methyl methacrylate) (PMMA) has been studied in a pyrolysis plant provided with a conical spouted bed reactor. This reactor is an interesting technology for the pyrolysis of waste plastics due to its excellent hydrodynamic behaviour and its high heat transfer and versatility. A previous kinetic study was carried out in thermobalance, in which the degradation of this polymer was observed to begin at low temperatures, 553 K. Consequently, the activation energy is low compared to other plastics. The influence of temperature on pyrolysis product distribution in the conical spouted bed reactor has been studied in the 673–823 K range. The products obtained at low temperatures are mainly the monomers of the polymer used for the study methyl methacrylate (MMA) and ethyl acrylate (EA). When the pyrolysis temperature is increased, the yield of monomers is lower due to the higher severity of secondary reactions, and there is a significant increase in the yield of gases. The maximum monomer recovery has been obtained at 673 K, with the yields of MMA and EA being 86.5% and 6.2%, respectively.     

Production of anorthite refractory insulating firebrick from mixtures of clay and recycled paper waste with sawdust addition

Production of porous anorthite refractory insulating firebricks from mixtures of two different clays (K244 clay and fireclay), recycled paper processing waste and sawdust addition are investigated. Suitability of alkali-containing-clay, low-alkali fireclay, pore-making paper waste and sawdust in the products was evaluated. Prepared slurry mixtures were shaped, dried and fired. Highly porous anorthite ceramics from the mixtures with up to 30% sawdust addition were successfully produced. Physical properties such as bulk density, apparent porosity, percent linear change were investigated as well as the mechanical strengths and thermal conductivity values of the samples. Thermal conductivities of the samples produced from fireclay and recycled paper waste decreased from 0.25 W/mK (1.12 g/cm³) to 0.13 W/mK (0.64 g/cm³) with decreasing density. Samples were stable at high temperatures up to 1100 °C, and their cold strength was sufficiently high. The porous anorthite ceramics produced in this study can be used for insulation in high temperature applications.