Syngas Production from Lignite Coal Using K2CO3 Catalytic Steam Gasification with Controlled Heating Rate in Pyrolysis Step

Gasification uses steam increases H2 content in the syngas. Kinetics of gasification process can be improved by using K₂CO₃ catalyst. Controlled heating rate in pyrolysis step determines the pore size of charcoal that affects yield gas and H₂ and CO content in the syngas. In previous research, pyrolisis step was performed without considering heating rate in pyrolysis step. This experiment was performed by catalytic steam gasification using lignite char from pyrolysis with controlled heating rate intended to produce maximum yield of syngas with mole ratio of H₂/CO ≈ 2. Slow heating rate (3 °C/min) until 850 °C in the pyrolysis step has resulted in largest surface area of char. This study was performed by feeding Indonesian lignite char particles and K₂CO₃ catalyst into a fixed bed reactor with variation of steam/char mole ratio (2.2; 2.9; 4.0) and gasification temperature (750 °C, 825 °C, and 900 °C). Highest ratio of H₂/CO (1.682) was obtained at 750 °C and steam/char ratio 2.2. Largest gas yield obtained from this study was 0.504 mol/g of char at 900 °C and steam/char ratio 2.9. Optimum condition for syngas production was at 750 °C and steam/char mole ratio 2.2 with gas yield 0.353 mol/g of char and H₂/CO ratio 1.682.     

Evaluation of the porous structure development of chars from pyrolysis of rice straw: Effects of pyrolysis temperature and heating rate

The effects of pyrolysis temperature and heating rate on the porous structure characteristics of rice straw chars were investigated. The pyrolysis was done at atmospheric pressure and at temperatures ranging from 600 to 1000 °C under low heating rate (LHR) and high heating rates (HHR) conditions. The chars were characterized by ultimate analysis, field emission scanning electron microscope (FESEM), helium density measurement and N₂ physisorption method. The results showed that temperature had obvious influence on the char porous characteristics. The char yield decreased by approximately 16% with increasing temperature from 600 to 1000 °C. The carbon structure shrinkage and pore narrowing occurred above 600 °C. The shrinkage of carbon skeleton increased by more than 22% with temperatures rising from 600 to 1000 °C. At HHR condition, progressive increases in porosity development with increasing pyrolysis temperature occurred, whereas a maximum porosity development appeared at 900 °C. The total surface area (S_total) and micropore surface area (S_micro) reached maximum values of 30.94 and 21.81 m²/g at 900 °C and decreased slightly at higher temperatures. The influence of heating rate on S_total and S_micro was less significant than that of pyrolysis temperature. The pore surface fractal dimension and average pore diameter showed a good linear relationship.     

Pyrolysis of textile wastes: I. Kinetics and yields

Thermal behavior of textile waste was studied by thermogravimetry at different heating rates and also by semi-batch pyrolysis. It was shown that the onset temperature of mass loss is within 104–156 °C and the final reaction temperature is within 423–500 °C. The average mass loss is 89.5%. There are three DTG peaks located at the temperature ranges of 135–309, 276–394 and 374–500 °C, respectively. The first two might be associated with either with decomposition of the hemicellulose and cellulose or with different processes of cellulose decomposition. The third peak is possibly associated to a synthetic polymer. At a temperature of 460 °C, the expected amount of volatiles of this waste is within 85–89%. The kinetic parameters of the individual degradation processes were determined by using a parallel model. Their dependence on the heating rate was also established. The pyrolysis rate is considered as the sum of the three reaction rates. The pyrolysis in a batch reactor at 700 °C and nitrogen flow of 60 ml/min produces 72 wt.% of oil, 13.5 wt.% of gas and 12.5 wt.% of char. The kinetic parameters of the first peak do not vary with heating rate, while those of the second and the third peak increase and decrease, respectively, with an increasing heating rate, proving the existence of complex reaction mechanisms for both cases.     

Pyrolysis of wood impregnated with phosphoric acid for the production of activated carbon: Kinetics and porosity development studies

The pyrolysis of impregnated wood for the production of activated carbon is investigated. Laboratory experiments are performed in a TG for heating rates of 10 °C/min and 20 °C/min and a mathematical model for the kinetics of the pyrolysis process is developed and validated. The effect of the temperature and of the time duration of the pyrolysis process on the specific surface of the activated carbon is examined on the basis of experiments conducted in a crossed bed reactor. Results indicate that the temperature and the residence time in the pyrolysis reactor may be optimised. Indeed, it is found that the maximum specific surface of the end product is obtained for pyrolysis processes conducted at a temperature of 400 °C for a time period of 1 h.     

Characterization of the different fractions obtained from the pyrolysis of rope industry waste

A study of the possibilities of pyrolysis for recovering wastes of the rope's industry has been carried out. The pyrolysis of this lignocellulosic residue started at 250 °C, with the main region of decomposition occurring at temperatures between 300 and 350 °C. As the reaction temperature increased, the yields of pyrolyzed gas and oil increased, yielding 22 wt.% of a carbonaceous residue, 50 wt.% tars and a gas fraction at 800 °C. The chemical composition and textural characterization of the chars obtained at various temperatures confirmed that even if most decomposition occurs at 400 °C, there are some pyrolytic reactions still going on above 550 °C. The different pyrolysis fractions were analyzed by GC–MS; the produced oil was rich in hydrocarbons and alcohols. On the other hand, the gas fraction is mainly composed of CO₂, CO and CH₄. Finally, the carbonaceous solid residue (char) displayed porous features, with a more developed porous structure as the pyrolysis temperature increased.     

Catalytic stepwise pyrolysis of packaging plastic waste

In this paper the combination of catalytic and stepwise pyrolysis is explored. A mixture of polyethylene (PE), polypropylene (PP), polystyrene (PS), poly(ethylene terephthalate) (PET) and poly(vinyl chloride) (PVC), which resembles real municipal plastic waste, has been pyrolysed in a 3.5 dm³ semi-batch reactor at 440 °C for 30 min using a ZSM-5 zeolite as catalyst. A low temperature (300 °C) dechlorination step has been carried out both with and without catalyst. It has been proved that the application of such dechlorination step gives rise to a 75 wt% reduction of chlorine in the liquid fraction. However, such step has a negative influence on the catalyst, which loses some catalytic activity. The optimum procedure in terms of quality and chlorine content of the products is the combination of first a low temperature step without catalyst, and second the catalytic pyrolysis step.     

H2 enriched fuels from co-pyrolysis of crude glycerol with biomass

Pyrolysis of glycerol has been identified as a possible route for producing high added value fuels like renewable hydrogen (H₂). Crude glycerol (CG) is the main byproduct of biodiesel industry and without purification it is a low added value material due to the presence of impurities. Co-pyrolysis of CG with biomass may improve the efficiency of the process and as a primary step of gasification give important information concerning the maximization of H₂ concentration in the produced gas. Moreover, the thermochemical treatment of crude glycerol–biomass mixtures may offer several economic and environmental advantages in biodiesel industry and reduce the cost of biodiesel production. A mixture of CG with olive kernel (OK) was used as pyrolysis feed material. Pyrolysis of a 25 wt% mixture of CG with OK at high temperature (T = 720 °C) seemed to promote steam reforming reactions leading to an increase of H₂ concentration of 11.6 vv% in the pyrolysis gas in comparison to H₂ in gas obtained by low temperature pyrolysis (T = 520 °C).     

High-pressure gasification reactivity of biomass chars produced at different temperatures

The knowledge of biomass char gasification kinetics is of considerable importance in the design of advanced biomass gasifiers, some of which operate at high pressures. In the present work the effects of pyrolysis temperature, total pressure and CO₂ concentration on the gasification of biomass chars have been studied using the thermogravimetric approach. The chars were obtained by pyrolysis in a drop tube furnace reactor at temperatures of 1000 and 1400 °C. The gasification tests were carried out in a pressurized thermogravimetric analyser (PTGA) at different temperatures, pressures and CO₂ concentrations. The reactivity measurements were conducted under the kinetically controlled regime, and three nth-order kinetic models as well as the Langmuir–Hinshelwood model were applied to determine the kinetic parameters.     

Study on the gas evolution and char structural change during pyrolysis of cotton stalk

The gas release properties and char structural evolution during the pyrolysis of cotton stalk were investigated. The evolution characteristics of volatile products were examined by pyrolysis–Fourier transform infrared spectroscopy (FTIR)/thermal conductivity detection (TCD) analysis (Py–FTIR/TCD). The char chemical structure and physical characteristics were investigated by means of FTIR and N₂ physisorption techniques. Evolution characteristics of the main volatile products were given. The evolution of CO₂ was approximately 26 °C earlier than that of CO. CH₄ evolution covered over a wider temperature range of 300–600 °C, with a maximum at 394 °C. The amount of hydroxyl, aliphatic CH and olefinic CC bonds in the char decreased significantly above 250 °C. The aromatization process started at ≈350 °C and continued to higher temperatures, leaving the char enriched with condensed aromatic ring systems. The BET surface area increased continually with increasing temperature to reach a maximum value of 4.68 m²/g at 500 °C and decreased at higher temperatures. The micropore volume showed a similar behavior to the surface area, while the mesopore volume and total pore volume always increased.     

Upgrading of woody biomass by torrefaction under pressure

In this study, the upgrading by torrefaction of leucaena, woody biomass, at 200–250 °C under volumetric pressure up to 4 MPa was examined. It was found that the yield of torrefied leucaena decreased with the increase in torrefaction temperature, whereas at the same temperature the yield of torrefied leucaena increased with the increase in torrefaction pressure. From the elemental analyses, the higher carbon content in torrefied leucaena can be achieved by the rising of torrefaction pressure. As large as 92.6% of carbon was recovered in the torrefied leucaena prepared at 250 °C and 4 MPa. On the other hand, the oxygen content decreased to 31.1% for the leucaena torrefied at 250 °C and 4 MPa. The higher heating value (HHV) of leucaena torrefied at high pressure increased significantly when compared to that of leucaena torrefied at atmospheric pressure. As large as 94.3% of energy yield was achieved with the mass yield of 74.4% for the torrefaction at 250 °C and 4 MPa. From the subsequent pyrolysis and combustion in TGA, leucaena torrefied under pressure showed the difference of weight decreasing curves comparing to that of leucaena torrefied at atmospheric pressure. It was found that the weight of leucaena torrefied at high pressure started to decrease at temperature lower than 200 °C. The char yield at 800 °C for the leucaena torrefied at high pressure increased with the increase in torrefaction pressure. These results suggested that the structure of leucaena was changed by the torrefaction under pressure and the cross-linking reactions during the pyrolysis were enhanced by the pressure during the torrefaction resulting in increase in char yields. The substantial increase in char combustion rate was also found for leucaena torrefied under pressure.     

Syngas production from pyrolysis–catalytic steam reforming of waste biomass in a continuous screw kiln reactor

A two-stage continuous screw-kiln reactor was investigated for the production of synthesis gas (syngas) from the pyrolysis of biomass in the form of waste wood and subsequent catalytic steam reforming of the pyrolysis oils and gases. Four nickel based catalysts; NiO/Al₂O₃, NiO/CeO₂/Al₂O₃, NiO/SiO₂ (prepared by an incipient wetness method) and another NiO/SiO₂ (prepared by a sol–gel method), were synthesized and used in the catalytic steam reforming process. Pyrolysis of the biomass at a rapid heating rate of approximately 40 °C/s, was carried out at a pyrolysis temperature of 500 °C and the second stage reforming of the evolved pyrolysis gases was carried out with a catalytic bed kept at a temperature of 760 °C. Gases were analysed using gas chromatography while the fresh and reacted catalyst was analysed by scanning electron microscopy, thermogravimetric analysis, transmission electron microscopy with energy dispersive X-ray and X-ray photoelectron spectroscopy. The reactor design was shown to be effective for the pyrolysis and catalytic steam reforming of biomass with a maximum syngas yield of 54.0 wt.% produced when the sol–gel prepared NiO/SiO₂ catalyst was used, which had the highest surface area of 765 m² g⁻¹. The maximum H₂ production of 44.4 vol.% was obtained when the NiO/Al₂O₃ catalyst was used.     

Conventional and microwave induced pyrolysis of coffee hulls for the production of a hydrogen rich fuel gas

This paper describes the conventional and microwave-assisted pyrolysis of coffee hulls at 500, 800 and 1000 °C. The influence of the pyrolysis method and temperature on the product yields and on the characteristics of the pyrolysis products is discussed. It was found that the pyrolysis of this particular residue gives rise to a larger yield of the gas fraction compared to the other fractions, even at relatively low temperatures. A comparison of microwave-assisted pyrolysis and conventional pyrolysis showed that microwave treatment produces more gas and less oil than conventional pyrolysis. In addition, the gas from the microwave has much higher H₂ and syngas (H₂ + CO) contents (up to 40 and 72 vol.%, respectively) than those obtained by conventional pyrolysis (up to 30 and 53 vol.%, respectively), in an electric furnace, at similar temperatures. From the pyrolysis fraction yields and their higher heating values it was found that the energy distribution in the pyrolysis products decreases as follows: gas > solid > oil. Moreover, the energy accumulated in the gas increases with the pyrolysis temperature. By contrast, the energy accumulated in the char decreases with the temperature. This effect is enhanced when microwave pyrolysis is used.     

Synthetic Liquid Fuels Obtained by Thermolysis of Animal Waste

Modern methods of recycling organic waste are not considered viable today. Therefore, an important advantage of the proposed technology is to obtain mineral fuel products as an output. The technologies of high-temperature processing are based on thermal decomposition of waste without oxygen at high temperature. In pyrolysis, wastes are converted into gaseous, liquid and solid fuels. Thereby, the properties and composition of the liquid feedstock obtained by pyrolysis with a boiling temperature in the range of X.I. (38) - 180 °C, 180 - 320 °C and more than 320 °C were investigated. Residue with a boiling temperature over 320° C (52.4% vol.) is the main portion of the synthetic liquid fuels (SLF). It can be attributed to fuel oil grade 100 and used as boiler fuel or fuel oil additives according to the studied physicochemical parameters.     

Semivolatile and volatile compounds from the pyrolysis and combustion of polyvinyl chloride

Emissions evolved from the pyrolysis and combustion of polyvinyl chloride (PVC) were studied at four different temperatures (500, 700, 850 and 1000 °C) in a horizontal laboratory tubular quartz reactor in order to analyse the influence of both temperature and reaction atmosphere on the final products from thermal and oxidative reactions. It was observed that the CO₂/CO ratio increased with temperature. Methane was the only light hydrocarbon whose yield increased with temperature up to 1000 °C. Benzene was rather stable at high temperatures, but in general, combustion at temperatures above 500 °C was enough to destroy light hydrocarbons. Semivolatile hydrocarbons were collected in XAD-2 resin and more than 160 compounds were detected. Trends on polyaromatic hydrocarbon (PAH) yields showed that most had a maximum at 850 °C in pyrolysis, but naphthalene at 700 °C. Formation of chlorinated aromatics was detected. A detailed analysis of all isomers of chlorobenzenes and chlorophenols was performed. Both of them reached higher total yields in combustion runs, the first ones having a maximum at 700 °C and the latter at 500 °C. Pyrolysis and combustion runs at 850 °C were conducted to study the formation of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). There was more than 20-fold increase in total yields from pyrolysis to combustion, and PCDF yields represented in each case about 10 times PCDD yields.     

Utilization of Low-grade Iron Ore in Ammonia Decomposition

Due to its cleanliness, fast energy cycle, and convenience of energy conversion, hydrogen has been regarded as the new energy source. Conventional process to produce hydrogen yield large amount of CO as byproduct. Moreover, the hydrogen storage and transportation have become the drawbacks in hydrogen economy. Thus, there has been increased interest in the hydrogen transportation medium as alternatives from the conventional process to produce and transport hydrogen. Ammonia has drawn worldwide attention as the most reliable hydrogen transportation medium. Through the decomposition of ammonia, hydrogen and nitrogen gas were produces as the byproduct without any CO or CO₂ emission. In this experiment, the ore were introduced as the medium for ammonia decomposition. The ore were put into quartz tube reactor and were dehydrated at 400 °C for 1 hour, then hydrogen reduced for 2 hours before and undergone ammonia decomposition at 500-700 °C for 3 hours. The effects of temperature to the % conversion of ammonia decomposition were also studied. Ammonia decomposition at higher temperature gives higher conversion. As seen in the results, the NH₃ conversion decreased with increasing time and the value after 3 hours of reaction increased in the sequence of 500 °C<600 °C< 700 °C. During ammonia decomposition, nitriding of iron occurred. The relation between temperature and the nitriding potential, K_N is also investigated. The purpose of this study is to investigate the utilization of low-grade ore as medium for ammonia decomposition to produce hydrogen.     

Quality variations of poultry litter biochar generated at different pyrolysis temperatures

Producing biochar and biofuels from poultry litter (PL) through slow pyrolysis is a farm-based, value-added approach to recycle the organic waste. Experiments were conducted to examine the effect of pyrolysis temperature on the quality PL biochar and to identify the optimal pyrolysis temperature for converting PL to agricultural-use biochar. As peak pyrolysis temperature increased incrementally from 300 to 600 °C, biochar yield, total N content, organic carbon (OC) content, and cation exchange capacity (CEC) decreased while pH, ash content, OC stability, and BET surface area increased. The generated biochars showed yields 45.7–60.1% of feed mass, OC 325–380 g kg⁻¹, pH 9.5–11.5, BET surface area 2.0–3.2 m² g⁻¹, and CEC 21.6–36.3 cmol_c kg⁻¹. The maximal transformation of feed OC into biochar recalcitrant OC occurred at 500 °C, yet 81.2% of the feed N was lost in volatiles at this temperature. To produce agricultural-use PL biochar, 300 °C should be selected in pyrolysis; for carbon sequestration and other environmental applications, 500 °C is recommended.     

Bio-oil from Jackfruit Peel Waste

Fossil fuels such as petroleum, charcoal, and natural gas sources are the main energy sources at present, but considering their natural limitation in availability and the fact that they are not renewable, there exists a growing need of developing bio-fuel production. Biomass has received considerable attention as a sustainable feedstock that can replace diminishing fossil fuels for the production of energy, especially for the transportation sector. JackfruitwasteisabundantinIndonesiamake itpotentiallyas one of thegreenrefineryfeedstockforthe manufacture ofbio-fuel.As intermediate of bio-fuel,jackfruitpeelsisprocessed intobio-oil. Pyrolysis, a thermochemical conversion process under oxygen-absent condition is an attractive way to convert biomass into bio- oil.In this study, the pyrolysis experiments were carried out ina fixed-bedreactor at a range of temperature of400-600 °C, heating rate range between 10-50 °C/min, and a range of nitrogen flow between 2-4litre/min. The aims of this work were to explore the effects of pyrolysis conditions and to identify the optimum condition for obtaining the highest bio-oil yield.The effect of nitrogen flow rate and heating rate on the yield of bio-oil were insignificant. The most important parameter in the bio-oil production was the temperature of the pyrolysis process.The yield of bio-oil initially increased with temperature (up to 550 °C) then further increase of temperature resulting in the decreased of bio-oil yield. Results showed that the highest bio-oil yield (52.6%)wasobtainedat 550 °C with nitrogen flow rate of 4L/min and heating rate of 50 °C/min. The thermal degradation of jackfruit peel was also studied using thermogravimetric analysis (TGA). Gas chromatography (GC-MS) was used to identify the organic fraction of bio-oil. The water content in the bio-oil product was determined by volumetric Karl-Fischer titration. The physicochemical properties of bio-oil produced from pyrolysis of jackfruit peels such as gross calorific value, pH, kinematic viscosity, density, sulfur content, ash content, pour point and flash point were determined and compared to ASTM standard of bio-oil (ASTM 7544).     

Pyrolysis of biocollagenic wastes of vegetable tanning. Optimization and kinetic study

Three solid wastes generated from the vegetable tanning of bovine skin in the Leather Industry (shavings, trimmings and buffing dust) were mixed together in the same proportions in which they were produced and the mixture was then used as a pyrolysis precursor for this research study. The optimal pyrolysis conditions for obtaining energy from the generated fractions (char, tar and gas fraction), and the preparation of activated carbons from the carbonaceous material (char), were established. The final conditions were chosen from two different points of view, the thermogravimetric results (TG/DTG) obtained at different heating rates (2–20 °C/min) and an optimization of the pyrolysis parameters by means of experiments carried out in a conventional furnace. The pyrolysis conditions finally selected were: heating rate (5 °C/min), final temperature (750 °C), and time at final temperature (60 min) and inert gas flow (N₂ 150 ml/min). The carbonaceous material (char) obtained exhibits good properties as a solid fuel due to its high calorific value and relatively low ash content. It also shows suitable characteristics as a precursor for the preparation of activated carbons. The condensable fraction has a predominantly phenolic nature and contains significant amounts of nitrogen compounds (nitriles, diketopiperazines, etc.), alkanes, alkenes, acids and esters, derived from the decomposition of tannins and collagen, with possible industrial applications in the preparation of chemical products. The gaseous phase is rich in carbon monoxide and carbon dioxide, and also contains a certain amount of methane and hydrogen. The syngas content increases with the pyrolysis temperature. A kinetic study of the pyrolysis was carried out using a model of independent reactions. The variation in the heating rate produced a slight shift to higher temperatures of the decomposition peaks, although this did not significantly affect either the kinetic parameters of the degradation processes or the percentage weight losses.     

Pyrolysis of sweet orange (Citrus sinensis) dry peel

Three different products were obtained from the pyrolysis of dry peel sweet orange: bio-oil, char and non-condensable gases. The yield of each product was determined. The bio-oil was characterized by GC–MS to determine that can be used as a renewable source of valuable industrial chemicals or as a source of energy, high heating value was calculated by Channiwala and Parikh correlation based on Dulong's Formula.Thermogravimetric analysis at 1, 5, 10, 20, and 40 °C/min, shows three different overlapped steps resulting in an average mass loss of ∼80% within the temperature range of 114–569 °C. The bench scale pyrolysis experiments, produces average yields of 53.1, 21.1 and 25.8 wt.% for bio-oil, char and gases, respectively. Bio-oil characterization by GC–MS and FTIR identified limonene as its main component while other identified compounds included δ-limonene, alcohols, phenols, benzene, toluene, xylene and carboxylic acids.     

Kinetic study of low-temperature conversion of plastic mixtures to value added products

Batch-mode pyrolysis of 200.0 g samples of polymers was studied at low temperature. The cracking reaction was carried out in a stainless-steel autoclave with reaction temperatures of 360, 380, 400 and 420 °C, initial pressure of 6.325 kPa (absolute pressure) and reaction times of 0–240 min. Based on the experimental results, a four-lump kinetic model has been developed to describe the production distribution of the light fractions, middle distillates and heavy fraction. This model reasonably fitted the results in each reaction of operation conditions. It was also found that the pyrolysis kinetics of separated plastic, mixed plastic and mixed plastic containing additives can be described by the same kinetic model. The plastic additives have not had a great influence on the product distribution and kinetics of the mixed plastic pyrolysis. Finally, the optimum conditions of low-temperature conversion of plastic mixtures to value-added products were established. The formation of heavy fractions from HDPE was as high as 70 wt% at 380 °C at a reaction time of 250 min. During the thermal degradation of plastic mixtures, the heavy fractions yielded up 50 wt% for 30 min reaction time at 400 °C. The total activation energies for the conversion of HDPE and the plastic mixtures were estimated to be 217.66 kJ mol⁻¹ and 178.49 kJ mol⁻¹, respectively.