Steam gasification reactivity of char from rapid pyrolysis of bio-oil/char slurry

A slurry of bio-oil and char originating from wood pyrolysis is a promising gasifier feed-stock because of its high energy density. When such a slurry is injected into a high temperature gasifier it undergoes a rapid pyrolysis yielding a char which then reacts with steam. The char produced by pyrolysis of an 80 wt% bio-oil/20 wt% char mixture at heating rates of 100-10,000 °C/s was subjected to steam gasification in a thermogravimetric analyzer. The original wood char from the bio-oil production was also tested. Gasification was conducted with 10-50 mol% steam at temperatures from 800 to 1200 °C. Reactivity of the slurry chars increased with pyrolysis heating rate, but was lower than that of the original chars. Kinetic parameters were established for a power-law rate model of the steam-char reaction, and compared to values from the literature. At temperatures over 1000 °C, the gasification rates appeared to be affected by diffusional resistance.     

The effect of coal particle size on pyrolysis and steam gasification

For future power generation from coal, one preferred option in the UK is the air-blown gasification cycle (ABGC). In this system coal particles sized up to 3 mm, perhaps up to 6 mm in a commercial plant, are pyrolysed and then gasified in air/steam in a spouted bed reactor. As this range of coal particle sizes is large it is of interest to investigate the importance of particle size for those two processes. In particular the relation between the coal and the char particle size distribution was investigated to assess the error involved in assuming the coal size distribution at the on-set of gasification. Different coal size fractions underwent different changes on pyrolysis. Smaller coal particles were more likely to produce char particles larger than themselves, larger coal particles had a greater tendency to fragment. However, for the sizes investigated in this study ranging from 0.5 to 2.8 mm, the pyrolysis and gasification behaviour was found not to vary significantly with particle size. The coal size fractions showed similar char yields, irrespective of the different char size distributions resulting from pyrolysis. Testing the reactivity of the chars in air and CO₂ did not reveal significant differences between size fractions of the char, nor did partial gasification in steam in the spouted bed reactor. From the work undertaken, it can be concluded that pyrolysis and gasification within the range of particle sizes investigated are relatively insensitive to particle size.     

Effects of pressure in coal pyrolysis observed by high pressure TGA

High-pressure thermogravimetric analyzer was employed to investigate the effects of pressure on the thermal decomposition process, which is the very first step in most coal utilizing processes, and pyrolyzates from TGA were analyzed by on-line GC/MS. Results showed that pyrolysis of coal with steam under high-pressure conditions exhibited a slower reaction rate compared to the lower pressure conditions, and the effect is more evident at the high temperature region. Coal rank also exhibited a distinct effect on the pyrolysis rate such that a subbituminous coal showed a bigger effect by steam-addition and pressure than bituminous coals. Weathered coal sample illustrated a slower reaction rate compared to the unoxidized coal. In addition, the implication of pressure effects on pyrolysis has been described.     

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.     

The char structure characterization from the coal reflectogram

Coal is a heterogeneous substance and its heterogeneity is identified and characterized by variation in reflectance. The main objective of this paper is to characterize the heterogeneity of char and to correlate it with the coal reflectogram, which accounts for both rank and maceral composition effects. Chars from two density fractions in a set of coals were obtained in a Drop Tube Furnace (DTF) at 1400 °C in N₂ environment. The chars were examined under a Scanning Electron Microscope (SEM) and the morphology information was obtained from the image-processing technique. The average porosity of char changes systematically with the FMR of its parent coals (defined as the summation of each reflectance multiplied with its frequency). The char porosity increased with an increase in FMR up to a critical value around 98. With further increase in FMR, the corresponding char becomes dense. The char macro porosity distribution was found to be related to the coal reflectogram. In general, the char porosity distribution shows two peaks, which corresponds to the inertinite and vitrinite peaks in reflectogram. The intensity depends on the maceral content. The relationship between the char porosity and coal reflectance for this set of sample has been found, which is strongly dependent on the coal rank. However, these findings cannot be applied to coals with a strong maceral association (microlithotype).     

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.     

Investigation on initial stage of rapid pyrolysis at high pressure using Taiheiyo coal in dense phase

Rapid pyrolysis of Taiheiyo coal was investigated with a laboratory-scale batch type reactor (BTR), which was specially developed to study various gasification processes at the conditions close to an industrial entrained bed gasifier. The experiments were carried out in helium at 1073 K, 7.1 MPa, varying reaction times from 1 to 80 s and coal/gas ratios in the range of 0.41-1.65 g/l. Extents of pyrolysis and profiles of product formation were discussed based on the results of char yield, gas and tar formation characteristics. It was observed that reaction of pyrolysis was significantly affected by coal/gas ratio. At high coal/gas ratios, pyrolysis was found to be retarded at initial stage. Pyrolysis products can be roughly divided into two groups. One is the ultimate products such as methane, carbon oxides, hydrogen, and benzene and the other is the intermediate products such as ethylene and toluene. Heat supply inside BTR was examined and the influence of thermal properties of atmospheric gases was investigated by carrying out pyrolysis in nitrogen and by comparing the results with that in helium. As a result, the heat capacity of atmospheric gas has less influence on pyrolysis process whereas heat conductivity of atmospheric gas as well as mixing conditions of gas and coal sample significantly affect the pyrolysis reaction.     

Experimental studies on gasification of the Shenmu coal char with CO2 at elevated pressures

The gasification rates of Shenmu coal chars with CO₂ were experimentally studied with a pressurized thermo- gravimetric analyzer (PTGA). Shenmu coal is a typical Chinese coal, and the coal char was prepared by a fixed-bed reactor in nitrogen at 900 °C. The experiments were carried out in the dynamic heating segments from 750 °C to 1,000 °C, and the reaction pressure increased from 0.1MPa to 3.1MPa with pure CO₂. The external diffusion resistances were minimized by increasing the flow rates and decreasing the thickness of sample layer before the test, to ensure the reactions were under kinetic control. The results show that the gasification rates increase proportionally to the 0.1 power of the CO₂ partial pressure. The unreacted-core shrinking model was applied to predict the reaction rate by changing the molar fraction of CO₂ at 0.6Mpa and 1.6Mpa total pressures, which showed a good match with experimental data. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Effect of pyrolysis temperature on the char micro-structure and reactivity of NO reduction

A phenol-formaldehyde resin (PFR) and a bituminous coal (SH) were pyrolyzed at various temperatures. The structure and the char-NO reactivity were analyzed in order to examine the effect of pyrolysis temperature on the micro-structure of the resulting char and further on the reactivity towards NO. Micro-structure of the char samples was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Raman spectroscopy. It was indicated that the micro-structure of PFR char and coal char experienced remarkable changes during pyrolysis, which resulted in the decrease of phenolic OH, aromatic hydrogen and more ordered structure. The pyrolysis temperature showed a weak impact on the reactivity of PFR char but comparatively remarkable impact on that of coal char at lower reaction temperature. Mineral matter in coal char presented a weak effect on the reactivity. This paper was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.     

Investigation of an iron-based additive on coal pyrolysis and char oxidation at high heating rates

Iron-based catalysts have been shown to enhance coal pyrolysis and char oxidation at low to moderate temperatures and heating rates (< 1250 K and 1–1000 K/s). Such catalytic activity has not been demonstrated at high heating rates and temperatures approaching pulverized coal combustion applications. The effect of an iron-based additive on coal pyrolysis and char combustion was studied in a flat-flame burner system at high particle heating rates using a Kentucky bituminous coal. Pyrolysis and char reactivity of two treated coals with different catalyst loadings were studied and compared with the untreated coal. The total volatiles yield for the treated coals increased between 14 and 18% (absolute) on a dry ash-free basis compared to the untreated coal in experiments conducted at 1300 K. A first-order char oxidation model was used to compare the apparent char reactivities of the treated and untreated coals measured at 1500 and 1700 K. An increase in apparent char reactivity was observed for both treated samples.     

Behavior of trace elements during pyrolysis of coal in a simulated drop-tube reactor

Release behavior and chemical form distribution of As, Pb, Cr, Cd and Mn in Datong coal during pyrolysis was studied in a simulated drop-tube reactor at a heating rate of about 1000 °C/s, including effects of temperature (300-1000 °C), atmosphere (N₂ and H₂), and holding time (0.3-10 min). Results show that the bleeding ratios of As, Pb, Cr, Cd and Mn increase with increasing pyrolysis temperature and holding time. Reductive environment results in higher emission of the elements. Among the five trace elements, As, Pb and Cd show similar behavior with volatilities higher than that of Cr and Mn at 1000 °C. The five trace elements in the coal and coal-derived chars are separated into five fractions through an extraction procedure. Ion exchangeable form of the elements is not found in the coal and the chars, and the elements remained in the residue fraction is the most dominant occurrence form in the coal and the chars for As, Pb, Cd and Cr. All the forms for all the elements undergo transformation in the pyrolysis resulting in reduced content in the chars.     

Study of the influence of pressure on enhanced gaseous hydrocarbon yield under high pressure-high temperature coal pyrolysis

The influence of pressure on the yield of gaseous hydrocarbon products derived from pyrolysis of Fushun and Xianfeng coals have been investigated in an anhydrous and confined system. Pyrolysis was performed in sealed gold tubes at 380 °C and under the pressures ranging from 50 to 250 MPa for 24 h. The results show that the effect of pressure on coal pyrolysis and product generation should not be ignored. For the Fushun and Xianfeng lignite, the yields of gaseous hydrocarbon generation increase by 9.1% and 12.7% when the pressure increases from 50 to 250 MPa, respectively. However, the yields of hydrogen gas decrease greatly with pressure. The hydrogen gas yields of Fushun and Xianfeng lignite decrease by 76.5% and 75.9%, respectively, when the pressure increases from 50 to 250 MPa. Yields of carbon dioxide gas of Fushun and Xianfeng coals were enhanced with increasing pressure by 7.4% and 8.9% respectively. Data of stable carbon isotope compositions reveal that the methane and ethane carbon isotope values are also affected by pressure, as they become heavier by approximately 1.2‰ (PDB) when the pressure is increased from 50 to 250 MPa. Simultaneously, the hydrogen isotope compositions of methane and ethane increase by 10.3‰ and 7.1‰, respectively. Our experimental results suggest that the increase in gaseous hydrocarbon yield is resulted from synthesis of carbon dioxide and hydrogen and pressure serves to facilitate the synthetic process.     

The reactions of formation of selected gas products during coal pyrolysis

Pyrolysis examinations conducted under non-isothermal conditions as well at low heating rate can show that the processes of hydrogen and methane formation are the result of several constituent reactions. In the presented paper a number of these reactions has been determined separately for each of the above mentioned gaseous products. The kinetic parameters of the reactions as well as the yields of products have also been calculated. It has been found that, during coal pyrolysis, methane is formed as a result of six constituent reactions and hydrogen is produced as a result of five constituent reactions. The values of activation energy and frequency factor for the reactions in question were determined. These values fall within the range, which is typical of chemical reactions.     

Char structural ordering during pyrolysis and combustion and its influence on char reactivity

In the present study, two processes, thermal treatment and oxidation, were separated for a fundamental study of structural evolution during pyrolysis and combustion, as well as for the study of the influence of such evolution on char reactivity. Chars were prepared at different temperatures and heating rates from a size-graded low volatile bituminous coal. The reactivity of resultant chars was measured in Kinetic Regime I using a fixed bed reactor. The structure of fresh and partly burnt chars was characterized using quantitative XRD analysis (QXRDA), high-resolution TEM (HRTEM), high-resolution FESEM, and multi-point gas adsorption.Both QXRDA and HRTEM observations show that char structure becomes more ordered with increasing pyrolysis temperature and decreasing heating rate. Char structure was also investigated as a function of char burnoff. The QXRDA results show that the amorphous concentration of char decreases during combustion while the aromaticity and average crystallite size of char increase. As a result, char structure becomes more ordered during combustion. This is in agreement with HRTEM observations. Due to the low reaction temperature (about 673 K), which is much lower than that for char preparation (1473 K), it was believed that oxidation, instead of thermal effect, contributed to the structural ordering observed during combustion. The structural parameters obtained from QXRDA were then correlated to char reactivity. Structural ordering was found to be responsible for char deactivation during thermal treatment and oxidation. Since the amorphous concentration and aromaticity of char are two strongest indicators of char reactivity, a structural disorder index, DOI, was defined based on them to describe char structural evolution, and further correlated to char reactivity.     

Decomposition and gasification of pyrolysis volatiles from pine wood through a bed of hot char

Pine wood was pyrolyzed in a fixed bed reactor at a heating rate of 10 °C and a final temperature of 700 °C, and the resultant volatiles were allowed to be secondarily cracked through a tubular reactor in a temperature range of 500-700 °C with and without packing a bed of char. The thermal effect and the catalytic effect of char on the cracking of tar were investigated. An attempt was made to deconvolute the intermingled contributions of the char-catalyzed tar cracking and the char gasification to the yields of gaseous and liquid products. It was found that the wood char (charcoal) was catalytically active for the tar cracking at 500-600 °C, while at 650-700 °C, the thermal effect became a dominant mode of the tar cracking. Above 600 °C, the autogenerated steam gasified the charcoal, resulting in a marked increase in the yield of gaseous product and a significant change in the gas composition. An anthracite char (A-char), a bituminous coal char (B-char), a lignite char (L-char) and graphite also behaved with catalytic activities towards the tar cracking at lower temperature, but only L-char showed reactivity for gasification at higher temperature.     

Modeling changes of fractal pore structures in coal pyrolysis

Coal pyrolysis processes are numerically investigated in mathematically produced coal pore models which simulate real coal pores in the parameters of the porosity and fractal dimension. The simulations include FG-DVC chemical reaction model, gas molecular diffusion in pores, energy conservation model and coal swelling model. Numerical results are verified by experimental results qualitatively, and they revealed that both the porosity and volatile contents of the parent coal can affect the fractal dimension of the final char pores after pyrolysis linearly. A formula to predict the fractal dimension of char pores from its parent coal properties is obtained by curve fitting in numerous results.     

Modelling of combustion characteristics of high ash coal char particles at high pressure: Shrinking reactive core model

Combustion of a single-particle high ash coal char at elevated pressure has been analyzed. A fully transient shrinking reactive core model incorporating a simple mechanistic kinetic scheme is used to study the combustion characteristics of high ash coal char. The model includes heat and mass transfer phenomena, reaction kinetics and intra-particle details. Finite volume method (FVM) has been used to solve partial differential equations representing fully transient conservation equations. The char combustion model predicts the mass-loss profile and burnout time of the char particle at different temperature and oxygen concentration. The computed results are found to agree well with the published experimental findings of pressurized combustion of high ash coal char. The effects of bulk temperature, total pressure and initial particle size on combustion characteristic and burnout time have been examined through model simulation.     

A comparison of basket willow and coal hydrogasification and pyrolysis

The presented work aimed at investigating the course of basket willow hydrogasification and comparing that process to the hydrogasification of bituminous coal. The examinations focussed on basket willow (Salix viminalis), bituminous coal of low degree of metamorphism and their blends at the mass ratio 1:1. Measurements of evolution kinetics of gaseous hydrocarbons during hydrogasification of those materials were conducted in the atmosphere of hydrogen under the pressure of 2.5 MPa. In the investigations, the non-isothermal method was employed. The examined samples were heated from ambient temperature up to 1200 K at the rate of 3 K/min.     

Preparation and rheology of biochar, lignite char and coal slurry fuels

Slurries of an Oil Mallee biomass char, a low rank coal char and sub-bituminous coals were prepared by mixing the finely milled solids with water and a range of additives including polyacrylic acid, charged copolymers D101 and D102, and sucrose. The resultant slurries were subjected to rheological characterizations including apparent viscosity and yield stress. The effect of the solid type, particle size distribution, and the additives on preparation of highly loaded slurries with the desired rheological behaviour were systematically examined in terms of apparent viscosity and yield stress. The additives D101 and D102 were found to be most effective in producing highly loaded suspensions with a low apparent viscosity and yield stress. Particle size distributions were manipulated to improve the solid loading. Suspensions produced by powder mixture containing equal weight precent of 30 min and 1 min milled powders gave a broad size distribution and is very effective in increasing the solid loading in slurries. The significant improvement in the solid loading was shown to be achieved by (i) increasing particle packing density via size distribution control and (ii) minimising the strength and number of the interactions between colloidal particles. The maximum solid loading of flowable (or relatively low apparent viscosity) slurries achieved with the Oil Mallee char is ∼40 wt.%, with the sub-bituminous coals 56-63 wt.%, and with the lignite char ∼65 wt.%. This study has shown that for low rank coals such as lignite, thermal and densification treatment is essential to achieve the solid loading of slurry fuel.     

Suppressing secondary reactions of coal pyrolysis by reducing pressure and mounting internals in fixed-bed reactor

Pyrolysis of Shenmu coal was performed in fixed-bed reactors indirectly heated by reducing operating pressure and mounting internals in the reactor to explore their synergetic effects on coal pyrolysis. Mounting internals particularly designed greatly improved the heat transfer inside coal bed and raised the yield of tar production.Reducing pressure further facilitated the production of tar through its suppression of secondary reactions occurring in the reactor. The absolute increase in tar yield reached 3.33 wt% in comparison with the pyrolysis in the reactor without internals under atmospheric pressure. The obtained tar yield in the reactor with internals under reduced pressure was even higher than the yield of Gray–King assay. Through experiments in a laboratory fixed bed reactor, it was also clarified that the effect of reducing pressure is related to volatile release rate in pyrolysis. It did not obviously vary tar yield at pyrolysis temperatures below 600 °C, while the effect was evident at 650 and 700 °C but became limited again above 800 °C. Under reduced pressure the produced tar contained more aliphatics and phenols but less aromatics.