Oxidation of a coal particle in flow of a supercritical aqueous fluid

A study was made of the conversion of single spherical coal particles of diameter 1–5 mm in a supercritical H₂O/O₂ fluid with an oxygen mass fraction of 0–6.6% in a semibatch reactor at a pressure of 30 MPa and a temperature of 673–1023 K. A decrease in the particle mass was observed in two parallel processes: gasification of coal with water and oxidation of coal with oxygen. An activation energy 19 ± 7 kJ/mole and a pre-exponential factor 10^−2±0.4 sec⁻¹ were obtained under the assumption of zero order for the concentration H₂O and an Arrhenius dependence for the rate of gasification with water. The oxidation with oxygen at a temperature above 780 K was found to be limited by the rate of O₂ diffusion to the coal organic matter. Below 780 K, the rate of heterogeneous oxidation with oxygen is described by a first-order reaction for the concentration of O₂ and a zero-order reaction for the concentration of H₂O with an activation energy of 150 ± 27 kJ/mole and a pre-exponential factor of 10^7.6±1.9 cm³/(g · sec). __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 2, pp. 23–31, March–April, 2008.     

Development of a pilot-scale acid gas removal system for coal syngas

The Korean pilot-scale gasification facility consists of a coal gasifier, hot gas filtering system, and acid gas removal (AGR) system. The syngas stream from the coal gasification at the rate of 100–120 Nm³/hr included pollutants such as fly ash, H₂S, COS, etc. The acid gas, such as H₂S and COS, is removed in the AGR system before generating electricity by gas engine and producing chemicals like Di-methyl Ether (DME) in the catalytic reactor. A hydrolysis system was installed to hydrolyze COS into H₂S. The designed operation temperature and pressure of the COS hydrolysis system are 150 °C and 8 kg/cm². After the hydrolysis system, COS was reduced below 1 ppm at the normal operating condition. The normal designed operation temperature and pressure of the AGR system are below 40 °C and 8 kg/cm². Fe-chelate was used as an absorbent. H₂S was removed below 0.5 ppm in the AGR system when the maximum concentration of H₂S was 900 ppm. A small scale COS adsorber was also installed and tested to remove COS below 0.5 ppm. COS was removed below 0.1 ppm after the COS adsorbents such as the activated carbon and ion exchange resin. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Simulation of DME synthesis from coal syngas by kinetics model

DME (Dimethyl Ether) has emerged as a clean alternative fuel for diesel. There are largely two methods for DME synthesis. A direct method of DME synthesis has been recently developed that has a more compact process than the indirect method. However, the direct method of DME synthesis has not yet been optimized at the face of its performance: yield and production rate of DME. In this study it is developed a simulation model through a kinetics model of the ASPEN plus simulator, performed to detect operating characteristics of DME direct synthesis. An overall DME synthesis process is referenced by experimental data of 3 ton/day (TPD) coal gasification pilot plant located at IAE in Korea. Supplying condition of DME synthesis model is equivalently set to 80 N/m³ of syngas which is derived from a coal gasification plant. In the simulation it is assumed that the overall DME synthesis process proceeds with steadystate, vapor-solid reaction with DME catalyst. The physical properties of reactants are governed by Soave-Redlich-Kwong (SRK) EOS in this model. A reaction model of DME synthesis is considered that is applied with the LHHW (Langmuir-Hinshelwood Hougen Watson) equation as an adsorption-desorption model on the surface of the DME catalyst. After adjusting the kinetics of the DME synthesis reaction among reactants with experimental data, the kinetics of the governing reactions inner DME reactor are modified and coupled with the entire DME synthesis reaction. For validating simulation results of the DME synthesis model, the obtained simulation results are compared with experimental results: conversion ratio, DME yield and DME production rate. Then, a sensitivity analysis is performed by effects of operating variables such as pressure, temperature of the reactor, void fraction of catalyst and H₂/CO ratio of supplied syngas with modified model. According to simulation results, optimum operating conditions of DME reactor are obtained in the range of 265–275 °C and 60 kg/cm². And DME production rate has a maximum value in the range of 1–1.5 of H₂/CO ratio in the syngas composition.     

Operation characteristics of 1 ton/day-scale coal gasifier with additional stage

A one-stage coal gasifier was modified to accommodate the two stages of coal feeding. Operating characteristics were compared between the one-stage and two-stage gasification in terms of syngas composition, carbon conversion, shape and inner structure of produced slags, characteristics of particle size distribution in entrained fines, and effects on particulate removal facilities. Temperature at the second stage of the gasifier resulted in lower values, which confirms the performance of the second stage as a reduction area by endothermic reactions. The results suggest that the 10–20% increase in coal feeding to the second stage might not cause much loss in carbon conversion. Produced slag and the performance of metal filters and water scrubber were similar with the earlier results from one-stage gasification tests. The two-stage gasification appears to help in increasing the cold gas efficiency for the certain operating range. Two-stage gasification had an impact on the 0.1–1 μm size of entrained fines, which appear to be cenospheres that occur during the rapid quenching in temperature.     

Carbon dioxide reforming of methane with a free energy minimization approach

Carbon dioxide reforming of methane to syngas is one of the primary technologies of the new poly-generation energy system on the basis of gasification gas and coke oven gas. A free energy minimization is applied to study the influence of operating parameters (temperature, pressure and methane-to-carbon dioxide ratio) on methane conversion, products distribution, and energy coupling between methane oxidation and carbon dioxide reforming methane. The results show that the methane conversion increases with temperature and decreases with pressure. When the methane-to-carbon dioxide ratio increases, the methane conversion drops but the H₂/CO ratio increases. By the introduction of oxygen, an energy balance in the process of the carbon dioxide reforming methane and oxidation can be realized, and the CO/H₂ ratio can be adjusted as well without water-gas shift reaction for Fischer-Tropsch or methanol synthesis. 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 operating conditions on gas components in the partial coal gasification with air/steam

With increasing environmental considerations and stricter regulations, coal gasification, especially partial coal gasification, is considered to be a more attractive technology than conventional combustion. Partial coal gasification was conducted in detail under various experimental conditions in a lab-scale fluidized bed to study the factors that affected gas components and heating value, including fluidized air flow rate, coal feed rate, and steam feed rate, gasification temperature, static bed height, coal type and catalyst type. The experiment results indicate that gasification temperature is the key factor that affects components and the heating value of gas is in direct proportion to gasification temperature. There exists a suitable range of fluidized air flow rate, coal feed rate, steam feed rate and static bed height, which show more complex effect on gas components. High rank bitumite coal is much more suitable for gasification than low rank bitumite coal. The concentrations of H₂, CO and CH₄ of bitumite coal are more than those of anthracite coal. Compounds of alkali/alkaline-earth metals, such as Ca, Na, K etc., enhance the gasification rate considerably. The catalytical effects of Na₂CO₃ and K₂CO₃ are more efficient than that of CaCO₃. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Synthesis of dimethyl ether from syngas obtained by coal gasification

The characteristics of a tubular fixed-bed reactor for the direct synthesis of dimethyl ether (DME) from syngas obtained by coal gasification have been developed. DME synthesis test was conducted with a hybrid DME synthesis catalyst (CuO/ZnO/Al₂O₃ for methanol forming, γ-alumina for methanol dehydration) to understand the performance under the conditions of 6.0MPa, 260°C and GHSV=3,000 l/kg-cat·h. The H₂ conversion and CO conversion were 85-92%, 37-45%, respectively. About 68-80% of DME selectivity was observed. DME synthesis reactor also operated at the productivity of 4.6-4.9 mol/kg-cat·h, which is slightly higher than that in the Peng’s prediction results in case of H₂ : CO=0.5.     

A study on the direct catalytic steam gasification of coal for the bench-scale system

Various techniques have been developed to increase the efficiency of coal gasification. The use of a catalyst in the catalytic-steam gasification process lowers the activation energy required for the coal gasification reaction. Catalytic-steam gasification uses steam rather than oxygen as the oxidant and can lead to an increased H₂/CO ratio. The purpose of this study was to evaluate the composition of syngas produced under various reaction conditions and the effects of these conditions on the catalyst performance in the gasification reaction. Simultaneous evaluation of the kinetic parameters was undertaken through a lab-scale experiment using Indonesian low rank coals and a bench-scale catalytic-steam gasifier design. The composition of the syngas and the reaction characteristics obtained in the lab- and bench-scale experiments employing the catalytic gasification reactor were compared. The optimal conditions for syngas production were empirically derived using lab-scale catalytic-steam gasification. Scale-up of a bench-scale catalytic-steam gasifier was based on the lab-scale results based on the similarities between the two systems. The results indicated that when the catalytic-steam gasification reaction was optimized by applying the K₂CO₃ catalyst to low rank coal, a higher hydrogen yield could be produced compared to the conventional gasification process, even at low temperature.     

CO2 gasification of Thai coal chars: Kinetics and reactivity studies

Two sized fractions (<75 μm and 150–250 μm) of Ban Pu lignite A and Lampang subbituminous B coals were pyrolyzed in a drop tube fixed bed reactor under nitrogen atmosphere at 500–900 °C. Gasification of coal chars with excess carbon dioxide was then performed at 900–1,100 °C. The result was analyzed in terms of reactivity index, reaction rate and activation energy. It was found that chars at lower pyrolysis temperature had highest carbon conversion, and for chars of the same sized fraction and at the same pyrolysis temperature, reactivity indices increased with gasification temperature. The lower rank Ban Pu lignite A had higher R _s values than higher rank Lampang subbituminous B coals. Smaller chars from both coals had higher R _s values, due to the higher ash content. At present, it can be concluded that, within the gasification temperature range studied, gasification rates of chars obtained at various pyrolysis temperatures showed a linear correlation with temperature. However, additional experiment is needed to verify the correlation.     

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     

Performance of a pilot-scale gasifier for Indonesian Baiduri coal

An entrained-bed slagging gasifier of 3 ton/day-class was constructed in 1995 and has operated in Korea ever since. A total of nine imported coals were tested to distinguish the gasification performance with coal characteristics under high pressure conditions. Through the tests, Indonesian Baiduri coal was selected as one of the most suitable coals for the gasifier due to its high reactivity, suitable ash fusion temperature, and low ash content. For the Baiduri coal, the gasifier yields more than 98% carbon conversion efficiency and above 80% cold gas efficiency while producing about 60% CO and 30% H₂ in the nitrogen-free basis. Results show that none of the heavy metal constituents in the produced slags by the gasification is leached out by water, which is a major advantage over any combustionbased processes where ash normally contains many leachable heavy components that may contaminate the under-ground water eventually. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Gasification of municipal solid waste in a pilot plant and its impact on environment

Municipal solid waste from three cities was gasified in a 3 ton/day capacity gasification/melting pilot plant based on Thermoselect at a temperature of around 1,200 °C using double inverse diffusion flame burner. The synthesis gas (syngas) obtained from gasification contains 25–34% CO and 28–38% of H₂. The high heating value of syngas was in the range of 10.88–14.65MJ/Nm³. Volatile organic compounds like furan, dioxin, and other organics in gaseous and liquid phase were effectively destroyed because of the high temperature of the high temperature reactor and shock cooling of syngas. Pollutants in exhaust gases were also found to be satisfying the Korean emission standard. Leaching concentration of heavy metals in the melted slag (vitrified mineral aggregate), fly ash, and treated water was much less than the Korean regulatory limit values due to high melting temperature (1,600 °C). The vitrified slag was of dark brown color. The glassy and amorphous nature of the vitrified mineral aggregate was further confirmed from SEM micrograph and XRD spectra of slag. The vitrified mineral aggregate could be used as natural raw material in cement and construction industry.     

Experimental studies of 1 ton/day coal slurry feed type oxygen blown, entrained flow gasifier

Experimental Studies of a 1 Ton/Day coal slurry feed type oxygen blown, entrained flow gasifier have been performed with the slurry concentration and gasifier temperature at 65% and above 1,300 ‡C, respectively. The characteristics of ash fusion temperature with addition of CaO as a flux were investigated to maintain the proper slag tapping condition in the range of reaction temperature. As the flux addition increased, ash fusion temperature showed a eutectic effect with the eutectic at around 20–30% CaO. In order to analyze the gasification characteristics, the effects of O₂/coal feed ratio on the product gas composition, heating value, gasifier temperature and cold gas efficiency were evaluated. From the results, it was shown in the case of Kideco coal that the cold gas efficiency was 44–60% and the heating value was 1,700-2,200 kcal/Nm³, while Drayton coal showed a cold gas efficiency of 55–62% and a heating value of 1,800-2,200 kcal/Nm³. In the case of Datong coal, the cold gas efficiency was 38–65%, and the heating value was 2,000-2,300 kcal/Nm³. Also, the results showed that the optimal operating condition of O₂/coal ratio for the three different coals was 0.9. Presented at the Int’/Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

煤气化费托合成/电联产系统建模及热力学分析

建立包括分布参数F-T合成反应器模型、考虑燃料气热值的燃气轮机模型及其他能够体现内部关键参数耦合关系的系统级单元子模型,并用于研究集成联产系统的整体热力学性能.首先,对合成气H2/CO、表观气速对F-T合成反应器合成气转化率和F-T合成尾气组成影响分析,结果表明F-T合成尾气存在CO/H2提高、CO2增浓的特点.综合考...     

Steam gasification of coal with salt mixture of potassium and nickel in a fluidized bed reactor

Australian coal loaded with a mixed catalyst of K₂SO₄+Ni(NO₃)₂ has been gasified with steam in a fluidized bed reactor of 0.1 m inside diameter at atmospheric pressure. The effects of gas velocity (2-5 U_g/U_mf), reaction temperature (750-900 °C), air/coal ratio (1.6-3.2), and steam/coal ratio (0.63-1.26) on gas compositions, gas yield and gas calorific value of the product gas and carbon conversion have been determined. The product gas quality and carbon conversion can be greatly improved by applying the catalyst; they can also be enhanced by increasing gas velocity and temperature. Up to 31% of the catalytic increment in gas calorific value could be obtained at higher temperatures. In the experimental runs with variation of steam/coal ratio, the catalytic increments were 16-38% in gas calorific value, 14-57% in carbon conversion, 5-46% in gas yield, and 7-44% in cold gas efficiency. With increasing fluidization gas velocity and reaction temperature, the unburned carbon fraction of cyclone fine for catalytic gasification decreased 4-18% and 13-16%, respectively, compared to that for non-catalytic gasification. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Sulfur transfers from pyrolysis and gasification of direct liquefaction residue of Shenhua coal

The sulfur transformation during pyrolysis and gasification of Shenhua direct liquefaction residue was studied and the release of H₂S and COS during the process was examined. For comparison, the sulfur transfer of Shenhua coal during pyrolysis and that of pyrolyzed char during gasification were also studied. The residue was pyrolyzed at 10 °C /min to 950 °C. During pyrolysis about 33.6% of sulfur was removed from the residue, among which 32.1% was formed H₂S in gas and 1.5% was transferred into tar, 66.4% of the sulfur was remained in residue char. Compared with coal, the residue has generated more H₂S due to presence of Fe_1−xS which was enriched in residue during liquefaction process. There is a few COS produced at 400-500 °C during pyrolysis of coal, but it was not detected form pyrolysis of the residue. During CO₂ gasification, compared with pyrolysis and steam gasification, there are more COS and less H₂S formation, because CO could react with sulfide to form COS. During steam gasification only H₂S was produced and no COS detected, because H₂ has stronger reducibility to form H₂S than CO. After steam gasification no sulfur was detected in the gasification residue. The XRD patterns show after steam gasification, only Fe₃O₄ is remained in the gasification residue. This indicates that the catalyst added during the liquefaction of coal completely reacted with steam, resulting in the formation of H₂ and Fe₃O₄.     

Laboratory-scale coal reactivity testing for entrained gasification

A relatively simple and rapid micro-gasification test has been developed for measuring gasification reactivities of carbonaceous materials under conditions which are more or less representative of an entrained gasification process, such as the Shell coal gasification process. Coal particles of < 100 μm are heated within a few seconds to a predetermined temperature level of 1000–2000 °C, which is subsequently maintained. Gasification is carried out with either CO₂ or H₂O. It is shown that gasification reactivity increases with decreasing coal rank. The CO₂ and H₂O gasification reactions of lignite, bituminous coal and fluid petroleum coke are probably controlled by diffusion at temperatures 1300–1400 °C. Below these temperatures, the CO₂ gasification reaction has an activation energy of about 100 kJ mol^?1 for lignite and 220–230 kJ mol^?1 for bituminous coals and fluid petroleum coke. The activation energies for H₂O gasification are about 100 kJ mol^?1 for lignite, 290–360 kJ mol^?1 for bituminous coals and about 200 kJ mol^?1 for fluid petroleum coke. Relative ranking of feedstocks with the micro-gasification test is in general agreement with 6 t/d plant results.     

Experimental research on air staged cyclone gasification of rice husk

A novel air cyclone gasifier of rice husk has been used to obtain experimental data for air staged gasification. Three positions and five ratios of secondary air were selected to study effect of the secondary air on the temperature profile in the gasifier and quality of syngas. Temperature profile and the syngas component are found to be strongly influenced by the injection position and ratio of the secondary air. Generally, gas temperature in all conditions increased at the early stage of reaction, and then decreased in the reduction zone where reactions were endothermic. The peak temperature in the gasifier changed with the injection positions and ratios of the secondary air, which could be as high as 1056 °C. The concentration of CO₂, CO, H₂ and CH₄ increased with the secondary air while the O₂ concentration remained constant. The syngas component exhibited different laws when the secondary air ratio was changed. It was also shown that the optimum condition was that the secondary air was injected in the oxidization zone at a secondary air ratio of about 31%. Under that condition, the fuel gas production was 1.30 Nm³/kg, the low heating value of the syngas was 6.7 MJ/Nm³, the carbon conversion rate was 92.2% and the cold gas efficiency of the gasifier was 63.2%. The tar content of the syngas was also studied in this paper. It decreased from 4.4 g/m³ for gasification without the secondary air to 1.6 g/m³ for gasification with the secondary air injected in the oxidization zone.     

高效能两段组合式煤气化过程热态试验

针对现有气流床气化技术在显热回收方面的不足,华东理工大学洁净煤技术研究所创新性开发煤基两段组合式气化工艺。在所建立的两段组合式煤气化炉热态试验装置上,考察了二段处理煤量和一段出口煤气组成对出口煤气热值、有效气浓度、二段碳转化率、水蒸气和二氧化碳转化率的影响。试验结果表明此气化工艺能有效利用一段炉煤气中的显热,提高气化炉出口煤气热值;二段适宜加入褐煤量为1400g,是一段处理量的10%;二段加煤量过多会降低二段煤层反应温度和促使焦油的生成;随着一段气化炉出口煤气所含水蒸气、CO2等气化剂浓度的增加,其对显热回收的作用就更明显;该工艺能减少CO2排放,具有良好的环境效益。     

Co-pyrolysis characteristics of coal and natural gas

A co-pyrolysis experiment of coal and natural gas was investigated on a fixed-bed reactor. SEM was used to study the structure changes of the exterior surface of char prepared in this co-pyrolysis experiment, while GC was also utilized to analyze the associated gas. The result showed that, with increasing temperature, the coal char tended to agglomerate. GC and SEM results show that the CH₄ decomposition on the exterior surface of char was turned to filamentous char and extended around like coral. It was also proved that the co-pyrolysis of coal and natural gas promoted syngas production. A synergistic effect of coal and natural gas does exist during this process. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.