Comparative investigations of coal pyrolysis under inert gas and H2 at low and high heating rates and pressures up to 10 MPa

Five German hard coals of 6–36 wt% volatile matter yield (maf) were pyrolysed at pressures up to 10 MPa, using two different apparatuses, which mainly differ in the heating rates. One consists of a thermobalance where a coal sample of ≈ 1.5 g is heated at a rate of 3 K min ^?1 under a gas flow of 3 I min^?1. The other apparatus is constructed for rapid heating (10²?10³ K s^?1) of a small sample of ≈10 mg of finely-ground coal distributed as a layer between the folded halfs of a stainless-steel screen, heated by an electric current. The product gas composition was determined by quantitatively analysing for H₂, CH₄, C₂H₄, C₂H₆, CO, CO₂ and H₂O. The amounts of tar and char were measured by weighing. The heating rate, pressure and gas atmosphere were varied. Under an inert gas atmosphere, high heating rates result in slightly higher yields of liquid products, e.g. tar. The yields of light hydrocarbon gases remain the same. With increasing pressure, the thermal cracking of tar is intensified resulting in high yields of char and light hydrocarbon gases. Under H₂, pyrolysis is influenced strongly at elevated pressure. Additional amounts of highly aromatic products are released by hydrogenation of the coal itself, particularly between 500 and 700°C. This reaction is less effective at higher heating rates because of the shorter residence time and diffusion problems of H₂. The yield of light gaseous compounds CH₄ and C₂H₆ increases markedly under either heating condition owing to gasification of the reactive char.     

Flash pyrolysis of coals. Devolatilization of bituminous coals in a small fluidized-bed reactor

The devolatilization behaviour of ten bituminous coals was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal particles being injected at a rate of 1–3 g h^?1 directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbon gases, and total volatile-matter and an agglomeration index are reported for all coals. Maximum tar yields were obtained at about 600 °C and were always substantially higher than those from the Gray-King assay. Total volatile-matter yields were also substantially higher than the proximate analysis values. The maximum tar yields appear to be directly proportional to the coal atomic $\text{H}\text{C}$ ratio. The elemental analysis of the tar is strongly dependent on pyrolysis temperature. The tar atomic $\text{H}\text{C}$ ratio is proportional to that of the parent coal. The effect on the devolatilization behaviour of two coals produced by changes in the pyrolyser atmosphere and the nature of the fluidized-bed material were also investigated. Substituting an atmosphere of hydrogen, helium, carbon dioxide or steam for nitrogen, has no effect on tar yield and, with one exception, little effect on the hydrocarbon gas yields. In the presence of hydrogen the yield of methane was increased at temperatures above 600 °C. Tar yields were significantly reduced on substituting petroleum coke for sand as the fluid-bed material. A fluidized bed of active char virtually eliminated the tar yield.     

Pyrolysis of tire powder: influence of operation variables on the composition and yields of gaseous product

The pyrolysis of tire powder was studied experimentally using a specially designed pyrolyzer with high heating rates. The composition and yield of the derived gases and distribution of the pyrolyzed product were determined at temperatures between 500 and 1000 °C under different gas phase residence times. It is found that the gas yield goes up while the char and tar yield decrease with increasing temperature. The gaseous product mainly consists of H₂, CO, CO₂, H₂S and hydrocarbons such as CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, C₄H₈ and C₄H₆ with a little other hydrocarbon gases. Its heating value is in the range of 20 to 37 MJ/Nm³. Maximum heating value is achieved at a temperature between 700 and 800 °C. The product distribution ratio of gas, tar and char is about 21:44:35 at 800 °C. The gas yield increases with increasing gas residence time when temperature of the residence zone is higher than 700 °C. The gas heating value shows the opposite trend when the temperature is higher than 800 °C. Calcined dolomite and limestone were used to explore their effect on pyrolyzed product distribution and composition of the gaseous product. It is found that both of them affect the product distribution, but the effect on tar cracking is not obvious when the temperature is lower than 900 °C. It is also found that H₂S can be absorbed effectively by using either of them. About 57% sulfur is retained in the char and 6% in the gas phase. The results indicated that high-energy recovery could not be achieved if fuel gas is the only target product. In view of this, multi-use of the pyrolyzed product is highly recommended.     

Devolatilization characteristics of high volatile coal in a wire mesh reactor

A wire mesh reactor was used to investigate the devolatilization process of coal particle during entrained flow gasification. Coal from Indonesia East Kalimantan mine, which has high moisture and high volatile matter, was chosen as a sample. Experiments were carried out at the heating rate of 1,000 °C/s and isothermal condition was kept at peak temperature under atmospheric pressure. The char, tar and gas formation characteristics of the coal as well as the composition of the gas components at peak temperatures were determined. The experimental results showed that devolatilization process terminated when temperature reached above 1,100 °C. Most of tar was formed at about 800 °C, while the rate of tar formation decreased gradually as the temperature increased. CH₄ was observed at temperatures above 600 °C, whereas H₂ was detected above 1,000 °C. The amount of formed gases such as H₂, CO, CH₄ and C _n H _m increased as the temperature increased. From the characteristics of devolatilization with residence time, it was concluded that devolatilization terminated within about 0.7 second when the temperature reached 1,000 °C. As the operating temperature in an entrained flow gasifier is higher than ash melting temperature, it is expected that the devolatilization time of high volatile coal should be less than one second in an entrained flow gasifier.     

Evaluation of utilization of corn stalks for energy and carbon material production by using rapid pyrolysis at high temperature

Pyrolysis of agricultural residues (corn stalks) took place batch wise in a laboratory captive sample reactor (wire mesh) at atmospheric pressure. The process was studied by varying the temperature (470-710 °C) with an average heating rate of 60 °C s⁻¹ and a reaction time of 0.2 s. The carrier gas used for both pyrolysis and GC analysis was He. The nature and quantity of gases produced and the main characteristics of the charcoals formed have been determined. From the GC analysis, CO showed the higher yield, followed by H₂, CH₄ and CO₂. The increase in temperature is especially important to increase the production of gas, mainly hydrogen. From gas composition and proximate analysis, the heating value of gas and solid phases has been determined. A kinetic model of pyrolysis based on first order kinetics and on total devolatilization has been developed. According to this model, kinetic constants, pre-exponential factors and activation energies have also been determined for low and high temperatures.     

Flash pyrolysis of coals. 1. Devolatilization of a Victorian brown coal in a small fluidized-bed reactor

The devolatilization behaviour of finely-ground (< 0.2 mm) Loy Yang brown coal was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal being fed at rates of 1–3 g/h directly into a bed of sand fluidized by nitrogen. Particle heating rates probably exceeded 10⁴ °C/s. The yields of tar, C₁-C₃ hydrocarbons and total volatile matter are reported for a pyrolyser-temperature range of 435 to 900 °C. A maximum tar yield of 23% w/w (dry ash-free coal), 60% more than the Fischer assay, was obtained at 580 °C. Yields of C₁-C₃ hydrocarbons increased with increasing temperature, reaching 8% at 900 °C. Elemental analyses showed that the composition of the tar and char products was strongly dependent on pyrolysis temperature. The effects on the devolatilization behaviour of the coal produced by the moisture associated with the coal, by hydrogen, and by the replacement of the sand by a fluidized bed of petroleum coke were investigated.     

Pyrolysis of peat: Product yield and characterization

Pyrolysis of peat obtained from Yeniça?a, Bolu, Turkey was conducted in a fixed-bed tube furnace under various conditions, and variations in the structure of the char, tar and gas products were examined. The chars produced were studied by proximate and ultimate analyses. The maximum tar yield of 20.41% was obtained at a heating rate of 20 °C/min, a temperature of 450 °C, a sweeping gas flow rate of 100 ml/min and a 0.5–2.0 mm size range. The chemical composition of the tar was examined by elemental analysis, FTIR spectroscopy, ¹H-NMR spectroscopy and column chromatography. The chemical composition of the tar with dense aliphatic structure was established to be CH_1.22O_0.25N_0.02. The composition of the gases obtained at a heating rate of 20 °C/min for the 0.5–2.0 mm size range was examined by gas chromatography.     

The effect of steam on pyrolysis and char reactions behavior during rice straw gasification

Steam gasification of biomass can generate hydrogen-rich, medium heating value gas. We investigated pyrolysis and char reaction behavior during biomass gasification in detail to clarify the effect of steam presence. Rice straw was gasified in a laboratory scale, batch-type gasification reactor. Time-series data for the yields and compositions of gas, tar and char were examined under inert and steam atmosphere at the temperature range of 873-1173 K. Obtained experimental results were categorized into those of pyrolysis stage and char reaction stage. At the pyrolysis stage, low H₂, CO and aromatic tar yields were observed under steam atmosphere while total tar yield increased by steam. This result can be interpreted as the dominant, but incomplete steam reforming reactions of primary tar under steam atmosphere. During the char reaction stage, only H₂ and CO₂ were detected, which were originated from carbonization of char and char gasification with steam (C + H₂O→CO + H₂). It implies the catalytic effect of char on the water-gas shift reaction. Acceleration of char carbonization by steam was implied by faster hydrogen loss from solid residue.     

Mechanisms and kinetics of homogeneous secondary reactions of tar from continuous pyrolysis of wood chips

The change of mass and composition of biomass tar due to homogeneous secondary reactions was experimentally studied by means of a lab reactor system that allows the spatially separated production and conversion of biomass tar. A tarry pyrolysis gas was continuously produced by pyrolysis of wood chips (fir and spruce, 10-40 mm diameter) under fixed-bed biomass gasification conditions. Homogeneous secondary tar reactions without the external supply of oxidising agents were studied in a tubular flow reactor operated at temperatures from 500 to 1000 °C and with space times below 0.2 s. Extensive chemical analysis of wet chemical tar samples provided quantitative data about the mass and composition of biomass tar during homogeneous conversion. These data were used to study the kinetics of the conversion of gravimetric tar and the formation of PAH compounds, like naphthalene.It is shown that, under the reaction conditions chosen for the experiments, homogeneous secondary tar reactions become important at temperatures higher than 650 °C, which is indicated by the increasing concentrations of the gases CO, CH₄, and H₂ in the pyrolysis gas. The gravimetric tar yield decreases with increasing reactor temperatures during homogeneous tar conversion. The highest conversion reached in the experiments was 88% at a reference temperature of 990 °C and isothermal space time of 0.12 s. Hydrogen is a good indicator for reactions that convert the primary tar into aromatics, especially PAH. Soot appears to be a major product from homogeneous secondary tar reactions.     

Flash pyrolysis of coals: influence of cations on the devolatilization behaviour of brown coals

The influence of cations on the pyrolysis behaviour of brown coals under flash heating conditions was investigated by means of a small fluidized-bed pyrolyser. A stream of coal particles in nitrogen was injected at rates of 1–3 g coal/h directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbons and total volatile matter from four Gelliondale brown coals and a Montana lignite were determined as a function of pyrolysis temperature. With all coals the maximum tar yield was obtained at 600 °C. Removal of cations present in the coals markedly increased the yields of tar and total volatile matter, with little effect on the yields of hydrocarbon gases. The converse was also observed in that the addition of Ca²⁺ to a cation-free coal decreased the yields of tar and total volatile matter. The extent of the reduction in tar yield at 600 °C in the presence of cations was found to be similar for all coals. After acid washing, tar yields appear to correlate with the atomic $\text{H}\text{C}$ ratios of the coals in a manner similar to that observed previously with bituminous coals.     

Gas evolution kinetics of two coal samples during rapid pyrolysis

Quantitative gas evolution kinetics of coal primary pyrolysis at high heating rates is critical for developing predictive coal pyrolysis models. This study aims to investigate the gaseous species evolution kinetics of a low rank coal and a subbituminous coal during pyrolysis at a heating rate of 1000 °C s^− 1 and pressures up to 50 bar using a wire mesh reactor. The main gaseous species, including H₂, CO, CO₂, and light hydrocarbons CH₄, C₂H₂, C₂H₄, C₂H₆, C₃H₆, C₃H₈, were quantified using high sensitivity gas chromatography. It was found that the yields of gaseous species increased with increasing pyrolysis temperature up to 1100 °C. The low rank coal generated more CO and CO₂ than the subbituminous coal under similar pyrolysis conditions. Pyrolysis of the low rank coal at 50 bar produced more gas than at atmospheric pressure, especially CO₂, indicating that the tar precursor had undergone thermal cracking during pyrolysis at the elevated pressure.     

Modeling circulating fluidized bed biomass gasifiers. Results from a pseudo-rigorous 1-dimensional model for stationary state

Results from a 1-dimensional and semirigorous model for atmospheric and circulating fluidized bed biomass gasifiers (CFBBGs), presented in the (previous) paper by Corella and Sanz [J. Corella, A. Sanz, Modeling circulating fluidized bed biomass gasifiers. A pseudo-rigorous model for stationary state. Fuel Process. Technol. 86 (2005) 1021–1053], are shown here. Process variables predicted by the model are gas composition (H₂, CO, CO₂, CH₄, C₂H_n, H₂O and O₂ contents), gas yield, tar content in the flue gas and char concentration in the solids. Both axial profiles in the riser and values at the gasifier exit are calculated from the model and are shown here for some selected sets of process variables. Variables analyzed in depth are: total air flow (used as equivalence ratio, ER), percentage of secondary air flow, height (location) of the secondary air flow, biomass moisture and biomass flow rate, expressed as the biomass weight hourly space velocity in the gasifier. All the results from the model agree both with known published data and with some tests made to check the model.     

Destruction of anthracene using a gliding arc plasma reformer

The gasification technology for biomass conversion has a limitation for some applications, including engines and turbines, because it produces tar-containing gas. In this study, a gliding arc plasma reformer was developed to remove tar. The plasma discharge in the gliding-type reformer is based on the both non-equilibrium and equilibrium plasmas. A simulation test was conducted using anthracene, which is produced during the gasification of biomass and waste, as the representative tar substance. In the optimal condition, the anthracene decomposition efficiency was 96.1%, and the energy efficiency was 1.14 g/kWh. The higher heating value of the gas produced from the anthracene decomposition was 11,324 kJ/Nm³, and the carbon balance was 98%. The steam flow rate, power input, total gas flow rate, and input concentration change were used as variables for the test. The anthracene decomposition efficiency was 81% when the gliding arc plasma reformer was used. When steam was fed at a rate of 0.63 L/min, the decomposition efficiency was highest (96.1%) due to the creation of OH radicals. The energy efficiency was highest (2.63 g/kWh) when the total gas flow rate was 24.1 L/min. H₂, CO, and CO₂ were produced as reformed gases. At the steam injection rate of 0.37 L/min or more, carbon black did not appear. Thus, it was verified that the gliding arc plasma reformer is effective for tar reduction.     

Influence of carrier gas flow and heating rates in fixed bed hydropyrolysis of coal

Fixed bed hydropyrolysis experiments on a UK bituminous coal (82% dmmf C) at 580–650 °C and pressures up to 300 bar have indicated that tar yields depend strongly on the velocity of the hydrogen carrier gas relative to the static coal particles. Tar yields increase with increasing pressure provided that the superficial gas velocity is not reduced. Otherwise, tar yields can actually decrease because the beneficial hydrocracking reactions that occur are no longer sufficient to counter the increased char formation resulting from the slower rates of intra-particle diffusion and devolatilization of tar molecules. While raising the heating rate from 1 to 20 °C s⁻¹ had little effect on overall conversions, hydrocarbon gas yields increased significantly at the expense of tar. Moreover, the higher heating rate gave more aromatic tars, and the available evidence strongly suggests that the primary volatiles are hydrocracked before escaping from the coal particles as well as in the vapour phase.     

Hydrogen production via gasification of meat and bone meal in two-stage fixed bed reactor system

Gasification of meat and bone meal followed by thermal cracking of tar was carried out at atmospheric pressure using a two-stage fixed bed reaction system in series. The first stage was used for the gasification and the second stage was used for thermal cracking of tar. In this work, the effects of temperature (650-850 °C) of both stages, equivalence ratio (actual O₂ supply/stoichiometric O₂ required for complete combustion) (0.15-0.3) and the second stage packed bed height (40-100 mm) on the product (char, tar and gas) yield and gas (H₂, CO, CO₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈) composition were studied. It was observed that the two-stage process increased hydrogen production from 7.3 to 22.3 vol.% (N₂ free basis) and gas yield from 30.8 to 54.6 wt.% compared to single stage. Temperature and equivalence ratio had significant effects on the hydrogen production and product distribution. It was observed that higher gasification (850 °C) and cracking (850 °C) reaction temperatures were favorable for higher gas yield of 52.2 wt.% at packed bed height of 60 mm and equivalence ratio of 0.2. The residence time of tar and product gases was varied by varying the packed bed height of second stage. The tar yield decreased from 18.6 wt.% to 14.2 wt.% and that of gas increased from 50.6 wt.% to 54.6 wt.% by changing the packed bed height of second stage from 40 to 100 mm while the gross heating value (GHV) of the product gas remained almost constant (16.2-16.5 MJ/m³).     

The Gibbs Free Energy Gradient Method for RDF gasification modelling

Starting from an equilibrium model for gasification, this research group has devised a new mathematical model, the so called Gibbs Free Energy Gradient Method Model (GMM). This model permits to bypass the semi-qualitative view, typical of equilibrium models, which assume very restrictive hypotheses such as equilibrium state for all the reactions involved in gasification process, complete conversion of carbon matter, gasification products in gas phase only. GMM model overcomes these limitations providing a quantitative point of view, even though the hypothesis of no tar production affects both models.GMM model has been applied to RDF gasification, supplying reliable results in the gasification process analysis. Model computations in terms of gas yield, gas composition, low heating value and H₂ yield, have been compared with literature results, showing that computed data are in good agreement with experimental ones.     

Partial oxidation reforming of biomass fuel gas over nickel-based monolithic catalyst with naphthalene as model compound

With naphthalene as biomass tar model compound, partial oxidation reforming (with addition of O₂) and dry reforming of biomass fuel gas were investigated over nickel-based monoliths at the same conditions. The results showed that both processes had excellent performance in upgrading biomass raw fuel gas. Above 99% of naphthalene was converted into synthesis gases (H₂+CO). About 2.8 wt% of coke deposition was detected on the catalyst surface for dry reforming process at 750 °C during 108 h lifetime test. However, no coke deposition was detected for partial oxidation reforming process, which indicated that addition of O₂ can effectively prohibit the coke formation. O₂ can also increase the CH₄ conversion and H₂/CO ratio of the producer gas. The average conversion of CH₄ in dry and partial oxidation reforming process was 92% and 95%, respectively. The average H₂/CO ratio increased from 0.95 to 1.1 with the addition of O₂, which was suitable to be used as synthesis gas for dimethyl ether (DME) synthesis.     

The fate of fuel-nitrogen during gasification of biomass in a pressurised fluidised bed gasifier

The distribution of fuel-nitrogen in gases, tar and char from gasification of biomass in a pressurised fluidised bed gasifier was investigated. Four species of biomass: birch, Salix, Miscanthus and Reed canary grass were gasified at 0.4 MPa and 900 °C. Oxygen-enriched nitrogen was used as fluidising agent. As a reference, gasification of Daw Mill coal was also carried out under the same experimental conditions. The experimental results illustrate that both the nature of the original fuels and the chemical structure of the nitrogen in the fuel have influence on the distribution of fuel-nitrogen in gases (NH₃, HCN, NO), tar and char under the employed experimental conditions. The present work also shows that the types of nitrogen heterocyclic compounds (NHCs) in the tar from different kinds of biomass are the same and the major compound is pyridine. However, the distribution of the various NHCs in the tar from the four species of biomass varies: the higher the content of fuel-nitrogen, the higher the concentration of two-ring NHCs in the tar. An effective method for extracting NHCs from the acidic absorption of the product gas was introduced in the present work. The method makes use of solid phase extraction (SPE) by a silica-based C₁₈ tube to extract the NHCs which subsequently were analysed by gas chromatography (GC) with flame ionisation detection (FID). The recovery and reproducibility of the SPE technique for NHCs is discussed.     

A predictive multi-step kinetic model of coal devolatilization

Devolatilization is the first step in coal combustion and gasification, thus an accurate kinetic modeling is relevant for the optimal design of these processes. In this work a relatively simple but flexible kinetic model is used to predict the thermal degradation of different coals in a wide range of operating conditions. The main feature of the model lies in its predictive capability: the elemental composition of the starting coal and the operating conditions are the only information required. Three reference coals are used to characterize the devolatilization process. The pyrolysis of each reference coal is described with a multi-step kinetic mechanism effective both at high and low heating rates. The devolatilization of the actual coal is simply obtained as a linear combination of the thermal degradation of the reference coals. The complete kinetic model refers to ∼30 reactions and lumped species, which makes this scheme suitable for being adopted in fluidynamic computations. A wide collection of comparisons between model prediction and experimental data validates this model both in terms of residual char and in terms of detailed gas and tar composition. The importance of secondary gas-phase reactions, mainly at high pressure, is also discussed and verified on the basis of an existing detailed kinetic scheme of pyrolysis and oxidation of hydrocarbon fuels.     

Synthesis gas and char production from Mongolian coals in the continuous devolatilization process

Devolatilization of Mongolian coal (Baganuur coal (BC), Shievee Ovoo coal (SOC), and Shievee Ovoo dried coal (SOC-D)) was investigated by using bench-sized fixed-bed and rotary kiln-type reactors. Devolatilization was assessed by comparing the coal’s type and dry basis, temperature, gaseous flux, tar formation/generation, devolatilization rate, char yield, heating value, and the components of the raw coal and char. In the fixed bed reactor, higher temperatures increased the rate of devolatilization but decreased char production. BC showed higher rates of devolatilization and char yields than SOC or SOC-D. Each coal showed inversely proportional devolatilization and char yields, though the relation was not maintained between the different coal samples because of their different contents of inherent moisture, ash, fixed carbon, and volatile matter. Higher temperatures led to the formation of less tar, though with more diverse components that had higher boiling points. The coal gas produced from all three samples contained more hydrogen and less carbon dioxide at higher temperatures. Cracking by multiple functional groups, steam gasification of char or volatiles, and reforming of light hydrocarbon gas increased with increasing temperature, resulting in more hydrogen. The water gas shift (WGS) reaction decreased with increasing temperature, reducing the concentration of carbon dioxide. BC and SOC, with retained inherent moisture, produced substantially higher amounts of hydrogen at high temperature, indicating that hydrogen production occurred under high-temperature steam. The continuous supply of steam from coal in the rotary kiln reactor allowed further exploration of coal gas production. Coal gas mainly comprising syngas was generated at 700–800 °C under a steam atmosphere, with production greatest at 800 °C. These results suggest that clean char and high value-added syngas can be produced simultaneously through the devolatilization of coal at lower temperature at atmospheric pressure than the entrained-bed type gasification temperature of 1,300–1,600 °C.