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.     

Colloidal structure of Victorian brown coals. 1. Alkaline digestion of brown coal

A mechanism is suggested for the alkaline digestion process. The proposed mechanism portrays the dissolution as a physicochemical disruption of the coal matrix by electrical-double-layer repulsion and movement of water molecules into the hydrogen-bonded network of the brown coal/water gel. The process is initiated by the reaction of hydroxyl ions with acidic functional groups in the coal, and involves the chemisorption of alkali-metal ions onto the coal structure. The coal particles are thus separated from one another, or ‘dissolved’, according to the steric orientation of the functional groups within the coal. The role of the alkali-metal ion has been confirmed by acid extraction and spectrophotometry.     

Colloidal structure of Victorian brown coals. 2. Rod-shaped particles in brown coal

Evidence is presented that brown coal contains rod-shaped particles of approximately one micrometre in diameter, and from 2 to 8 micrometres in length. Up to 42% of the coal can be obtained as rods by using alkali to separate them from larger lumps. Rods in alkaline suspension aggregate into bundles which were detected by sedimentation analysis and confirmed by microscopic examination. They have been found to have a low oxygen content, and are probably derived from the cell-wall component of coalified wood.     

Pyrolysis—gas chromatography of Australian coals. 1. Victorian brown coal lithotypes

Pyrolysis—gas chromatography (Py—g.c.) has been shown to be a useful technique for characterizing Victorian brown coal lithotypes. The pyrograms show marked changes in the predominance and distribution of specific molecular classes as a function of lithotype. Hydrogen-rich triterpenoid components are predominantly associated with the lighter lithotypes, whereas hydrogen-deficient phenolic components are more abundant in pyrolysates from the darker lithotypes. Carbon preference indices (CPIs) are >1 for the alkanes but <1 for the alkenes released by pyrolysis. All CPI values generally increase with darkening lithotype. Correlations of the components released with the maceral composition of the lithotypes have also been established. This information is used to establish some details of the mechanism of pyrolysis and the probable relative liquefaction behaviour of these lithotype samples.     

Flash pyrolysis of coals: behaviour of three coals in a 20 kg h−1 fluidized-bed pyrolyser

Flash pyrolysis of Loy Yang brown coal, and Liddell and Millmerran bituminous coals has been studied using a fluidized-bed reactor with a nominal throughput of 20 kg h^?1. The apparatus and its performance are described. The yields of tar and hydrocarbon gases are reported for each coal in relation to pyrolysis temperature, as also are analytical data on the pyrolysis products. The peak tar yields for the dry, ash-free Loy Yang and Millmerran coals were respectively 23% wt/wt (at ≈ 580 °C) and 35% wt/wt (at $\text{\$}\text{?}$600 °C). The tar yield from Liddell coal was 31% wt/wt at ≈ 580 °C. Hydro-carbon gases were produced in notable quantities during flash pyrolysis; e.g. Millmerran coal at 810 °C gave 6% wt/wt (daf) methane, 0.9% wt/wt ethane, 6% wt/wt ethylene, and 2.5% wt/wt propylene. The atomic $\text{H}\text{C}$ ratios and the absolute levels of hydrogen in product tars and chars decreased steadily with increasing pyrolysis temperature.     

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.     

Supercritical gas extraction of Victorian brown coals: The effect of coal properties

A selection of fifteen Victorian brown coals, which varied in lithotype but only slightly in rank, were subjected to supercritical gas extraction with toluene. Seven of these coals were also extracted with 5% tetralin/toluene under the same conditions of temperature and pressure (400 °C and 10 MPa). The overall conversion, the extract yield and the yield of toluene solubles (oil and asphaltene) were correlated with more easily obtained coal properties using simple linear regression analysis. Good correlations were obtained between the total conversions and the volatile matter content of the coals, and for the toluene extractions between both the extract yield and the yield of toluene solubles and the H/C atomic ratio. For the toluene solubles from the toluene extractions, the aromaticity decreased and the molecular weight increased as the H/C atomic ratio of the coal increased. Inorganic constituents of the coals did not appear to have a marked effect on total conversion and liquid yields. Removal of the cations from two coals increased conversion and liquid yields in one case and decreased these in the other, but in both instances the changes were not large.     

Kinetics of Colorado oil shale pyrolysis in a fluidized-bed reactor

Previous hydrocarbon evolution data were reanalysed to determine improved rate expressions for oil generation from Colorado oil shale under rapid pyrolysis conditions. Contributions from low-molecular-weight gases were subtracted from flame-ionization detector data to obtain the rate of oil generation alone. Equally good fits to the data were obtained using two parallel first-order reactions or a single reaction with an effective reaction order of 1.51. The latter expression was easier to incorporate into global process models. The rate expressions were independent of shale source (Anvil Points or Tract C-a) and particle size (0.5–2.4 mm). The kinetic data were consistent with the previous conclusion that the small incremental oil yield possible for fluidized-bed pyrolysis requires a longer residence time than that estimated by kinetic expressions derived from slow-heating data.     

Flash pyrolysis of wood in a cyclone reactor

This paper reports the first results of an experimental study of the continuous flash pyrolysis of wood sawdust in a cyclone reactor between 893 and 1330 K. The reaction produces low fractions of char (4%) and the gasification yield increases from 0% at about 800 K to 90% at around 1330 K with a constant volume fraction of CO and H₂ (≈73%) and an increasing fraction of light hydrocarbons (up to 50% mass fraction). The heating value of the gas reaches 19 000 kJ m⁻³ STP for the highest temperatures. The wood particles mainly heated by radiation and solid convection react in less than 1 s while the carrier gas (residence time of the order of 0.05 s) seems to be only weakly heated. The 46.2 × 10⁻⁶ m³ cyclone reactor can operate with excellent stability for wood flow rates up to 0.35 kg h⁻¹ at a wall temperature of 1330 K. The cyclone seems to be very efficient for carrying out reactions of the solid → fluids type but more accurate determination of process parameters such as gas and solid residence times and heat transfer efficiencies are required to gain a better understanding of the behaviour of such a high temperature reactor.     

Kinetics of steam gasification of nascent char from rapid pyrolysis of a Victorian brown coal

Steam gasification of nascent char from rapid or slow pyrolysis of a Victorian brown coal was performed at 1073–1173 K in a novel drop-tube/fixed-bed reactor, in which steam-containing gas was forced to pass through an extremely thin bed of nascent char particles at sufficiently high velocity and large flux. The nascent char underwent parallel reactions consisting of non-catalytic gasification and catalytic one. The non-catalytic gasification followed first-order kinetics with respect to the fraction of unconverted carbon, and the rate constant was hardly influenced by operating variables such as heating rate for the pyrolysis, total pressure and even period of isothermal heating between the pyrolysis and gasification. The overall activity of inherent catalysts, alkali and alkaline earth metallic species, diminished due to volatilization and intra-particle deactivation, both of which were induced by the gasification. As a result, the catalytic gasification took place within a limited range of the char conversion up to 60–80%. The initial catalyst activity and the kinetics of activity loss largely depended on the operating variables as above and also partial pressure of steam.     

High‐temperature pyrolysis and CO2 gasification of Victorian brown coal and Rhenish lignite in an entrained flow reactor

The low rank coals from Victoria, Australia, and Rhineland, Germany are of interest for use in entrained flow gasification applications. Therefore, a high temperature, electrically heated, entrained flow apparatus has been designed to address the shortage of fundamental data. A Victorian brown coal and a Rhenish lignite were subjected to rapid, entrained flow pyrolysis between 1100 and 1400°C to generate high surface area chars, which were subsequently gasified at the same temperatures under CO₂ in N₂ between 10 and 80 vol %. The Victorian coal was more reactive than the Rhenish coal, and peak char reactivity was observed at 1200°C. Char conversion and syngas yield increased with increasing temperature and plateaued at high CO₂ concentration. Ammonia and tar species were negligible and HCN and H₂S were present in parts per million (volume) concentrations in the cooled, filtered syngas. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2101–2111, 2016     

Hydroliquefaction of Victorian brown coal in a continuous reactor: 1. Effects of residence time,temperature and catalysts on conversion

Slurries of two, closely related, Victorian brown coal samples in tetralin (1:3) were reacted with hydrogen in a continuous reactor system both with and without the addition of iron and iron-tin-based catalysts. The conversion to liquid products was greater when the catalysts were ion-exchanged onto the coal rather than being added as powders and the previously observed trend of iron/tin giving greater conversion than iron was exhibited. Increased temperature and residence time increased the oil yield.     

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.     

Colloidal structure of Victorian brown coals. 3. Examination by ultracentrifugation

The particulate structure of brown coal has been studied in the hitherto little explored 1 nm- 1μm size range. To do this the coal was digested in alkali then filtered through a 1.2 μm membrane filter. The filtrate, which contained 31 wt % of the original coal, was centrifuged for various periods and speeds in a high speed ultracentrifuge equipped with a long-tube rotor. The particle size distribution determined in this way showed that there were no particles between about 5 nm and 1 μm in size, and that about 23 wt % of the total alkali-digested coal was smaller than 1 nm.     

Degradation of a Victorian brown coal in sub-critical water

Conversion characteristics of a Victorian brown coal in sub-critical water were investigated. Pulverized brown coal was heated up to 623 K in flowing sub-critical water pressurized at 25 MPa. The total conversion of the coal into extract and non-condensable gas reached over 70 wt%-daf, which was appreciably higher than the maximum conversion (50 wt%-daf) with a sub-critical non-hydrogen donor solvent, 1-methylnaphthalene (MN). Laser-ionization-desorption mass spectrometry showed that the sub-critical water extract was richer in lower-molecular-mass compounds than the sub-critical MN one. Thus, degradation of the coal occurred more extensively in sub-critical water than in MN. Along with the conversion in sub-critical water, both the total contents of hydrogen and phenolic hydroxyls in the whole products remained nearly unchanged. This suggests comparable and simultaneous formation and decomposition of hydroxyls through hydrolysis of ethers/esters and dehydration condensation between hydroxyls/carboxyls, respectively. For detecting the hydroxyl formation, the coal was first heated at 623 K under an inert gas atmosphere until the formation of water and the other volatiles was completed. Then, the heat-treated coal (LY-H) was exposed to flowing sub-critical water. As expected, the net formation of phenolic hydroxyls from LY-H was detected as 0.8 mmol-OH/g-LY-H while that of hydrogen as 2.3 mmol-H/g-LY-H. Approximately a half of the hydrogen gain was explained as phenolic hydroxyls gain, suggesting the importance of hydrolysis of esters and ethers that formed carboxyls and alcoholic hydroxyls as well as phenolic hydroxyls.     

Hydrotreating the bitumen-derived hydrocarbon liquid produced in a fluidized-bed pyrolysis reactor

The pyrolysis of bitumen-impregnated sandstone produces three primary product streams: C₁---C₄ hydrocarbon gases, a C₅⁺ total liquid product, and a carbonaceous residue on the spent sand. The bitumen-derived hydrocarbon liquid was significantly upgraded relative to the native bitumen: it had a higher API gravity, lower Conradson carbon residue, asphaltene content, pour point and viscosity, and a reduced distillation endpoint relative to the native bitumen. The elemental composition was little different from that of the native bitumen except for the hydrogen content, which was lower. Thus, integration of the bitumen-derived liquid into a refinery feedstock slate would require that it be hydrotreated to reduce the nitrogen and sulphur heteratom concentrations and to raise the atomic hydrogen-to-carbon ratio. The bitumen-derived liquid produced in a fluidized-bed reactor (diameter 10.2 cm) from the Whiterocks tar sand deposit has been hydrotreated in a fixed-bed reactor to determine the extent of upgrading as a function of process operating variables. The process variables investigated included total reactor pressure (11.0–17.2 MPa (1600–2500 psig)); reactor temperature (617–680 K; (650–765 °F)) and liquid hourly space velocity (0.18-0.77 h⁻¹). The hydrogen/oil ratio was fixed in all experiments at 890 m³ m⁻³ (5000 scf H₂/bbl). A sulphided Ni-Mo on alumina hydrodenitrogenation catalyst was used in these studies. The extent of denitrogenation and desulphurization of the bitumen-derived liquid was used to monitor catalyst activity as a function of process operating variables and to estimate the extent of catalyst deactivation as a function of time on-stream. The apparent kinetics for the nitrogen and sulphur removal reactions were determined. Product distribution and yield data were also obtained.     

The swelling and adsorption characteristics of Victorian brown coals

Samples of coals from the Latrobe Valley, Victoria, were exposed to certain gases and vapours, and the resulting swelling was measured by a novel technique using displacement of mercury. Methanol and acetone were found to be powerful swelling agents: carbon dioxide, at the pressures used (up to 100 k Pa) caused no measurable swelling. The carbon dioxide results are relevant to the measurement of surface areas of coals by carbon dioxide adsorption.     

Rheological behaviour of Victorian brown coal

As part of an investigation into the use of extrusion as a feed mechanism for processing very wet, soft, brown coals, a parallel plate plastometer was used to obtain absolute rheological data for Loy Yang coal which had been previously work-softened by shearing for various lengths of time. A Bingham model was found to describe the flow behaviour of the material adequately. Most of the resistance to deformation was found to be produced by viscous and not plastic stresses, from which it was concluded that the work-softening effect is a result of a decrease in Bingham viscosity. The fine structure of the coal is broken down by shearing and the water released as a consequence acts as a lubricant between the particles. The ruptured bonds do not remake on standing. It is concluded that any investigation of coal rheology, or the design of any industrial handling or processing operation in which coal rheology might be important, should take account of not only the total water content of the coal but also the disposition of that water. For example, coals with low water contents which would not be thought suitable for extrusion because of their apparent stiffness may be suitable if water can be liberated from the structure by shearing.