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.     

Roles of inherent metallic species in secondary reactions of tar and char during rapid pyrolysis of brown coals in a drop-tube reactor

Two pairs of raw and acid-washed coal samples were prepared from Yallourn and Loy Yang brown coals, and subjected to rapid pyrolysis in a drop-tube reactor at 1073-1173 K in a stream of N₂ or H₂O/N₂ mixture. Examinations were made on the roles of the inherent metallic species in the secondary reactions of nascent tar and char that were formed by the intraparticle primary reactions. The experimental results revealed that the inherent metallic species were essential for vary rapid steam reforming/gasification of the nascent tar/char and simultaneous suppression of soot formation. In the absence of the metallic species, the soot formation from the tar accounted as much as 15-19 and 6-13% of the carbon in coal in N₂ and H₂O/N₂, respectively. The metallic species reduced the yield of soot to 6-8% in N₂ by enhancing the reforming of tar by H₂O generated from the pyrolysis of coal. In the H₂O/N₂ stream, instead of soot formation, a net gasification conversion up to 17% within 4.3 s was observed in the presence of the metallic species as a result of catalytic gasification of the nascent char. Moreover, the metallic species catalyzed the steam reforming of the nascent tar, giving its conversion up to 99%. Over the range of the conditions employed, a one-to-one stoichiometry was established between the steam consumption and the yield of carbon oxides formed by the steam reforming/gasification and water-gas-shift reaction.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part X: Effects of volatile-char interactions on the conversion of coal-N during the gasification of a Victorian brown coal in O2 and steam at 800 °C

A novel fluidised-bed/fixed-bed reactor was used to study the effects of volatile-char interactions on the conversion of coal-N during the gasification of a Victorian brown coal at 800 °C. The reactor has the capability of controlling the extent and length of the interactions between volatiles and char. Our results indicate that in the absence of volatile-char interactions during gasification in O₂, the lack of abundant H radicals led to negligible formation of NH₃ and HCN from char-N. The presence of volatile-char interactions during the gasification of Victorian brown coal in O₂ at 800 °C drastically enhanced the formation of NH₃ and, albeit to a lesser extent, the formation of HCN. The enhanced conversion of char-N into NH₃ (and HCN) due to the volatile-char interactions is attributed to the presence of H radicals in the volatiles. H radicals in volatiles could “die off” as they pass through the nascent char bed during the course of volatile-char interactions.     

A new integrated approach of coal gasification: the concept and preliminary experimental results

The total carbon conversion of conventional fluidized bed gasifier is relatively low (<90%) mainly because of carbon loss in fly-ash. In this paper, a new concept of integrated coal gasification—fluidized bed+entrained flow is introduced. Within this process, large partition of coal with higher reactivity is converted in an ash agglomerating fluidized bed reactor under moderate temperature (~1000 °C). The remaining small partition of coal (fly-ash) with lower reactivity is converted in a small integrated entrained flow gasifier under higher temperature (1200–1400 °C). Low carbon content ash is withdrawn in dry mode by ash agglomerating, with no need to be melted. Preliminary experimental results show that the whole system can be operated steadily, total carbon conversion reaches >95%, efficient gas (CO+H₂) concentration is 78–82%. Heat exchange between two reactors has been realized, the high temperature gas from entrained flow gasifier can be cooled, and in the mean time the temperature of fluidized bed nearly keeps constant. The high-temperature ash from entrained flow gasifier can be cooled by the char in dense phase of the fluidized bed and then withdrawn in agglomerating mode. All these results prove the concept correct and feasible.     

Co-Combustion of Oil Sludge Char and Brown Coal in a Continuous Fluidized-Bed Combustor

For developing technologies for innocent disposal of/energy recovery from high-ash oil sludge char (OSC), it was continuously combusted in a 10 kg h⁻¹ fluidized-bed combustor. Addition of brown coal (BC) improved its combustion, but excessive BC was prone to cause slagging. Fine coke particles in OSC and volatiles in BC led to staged temperatures along the fluidized bed through air-staging co-combustion, enabling excellent combustion performance as well as efficient NO_x reduction, especially when coupled with selective non-catalytic reduction. Thus, there is a potential to cleanly recover energy from OSC by its co-combustion with BC.     

Entrained flow gasification of coal: 1. Evaluation of mixing and reaction processes from local measurements

Local mixing and reaction processes were studied within a laboratory-scale, entrained coal gasifier at atmospheric pressure, using a Utah high-volatile, low-sulphur bituminous coal at a design flow rate of 24.5 kg h⁻¹. The coal-oxygen-steam feed mass ratio was 1.00:0.91:0.27. A water-quenched sample probe was used to collect radial gas and char samples at seven different axial positions in the 124 cm long reactor for the measurement of gasification products and residual char composition. The observed carbon conversion was 79 ± 3%. Coal hydrogen and oxygen were converted more rapidly and more completely than carbon. Devolatilization, which occurred very rapidly near the inlet, led to most of this carbon conversion; heterogeneous char reactions with CO₂ and steam apparently accounted for the balance. Oxygen was consumed through reaction with volatiles very quickly in the upper gasifier region. These data were used to evaluate mixing and reaction characteristics within the reactor. Agreement of measurements with predictions from a generalized two-dimensional entrained coal gasification model was good.     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part III. The importance of the interactions between volatiles and char at high temperature

A novel two-stage fluidised-bed/fixed-bed reactor was designed to investigate the effects of volatile-char interactions on the volatilisation of alkali and alkaline earth metallic (AAEM) species during the pyrolysis of Victorian brown coal at 900 °C. With the two-stage reactor configuration, the AAEM-free volatiles generated from the pyrolysis of the H-form coal in the fluidised bed came into direct contact with the char from NaCl-loaded or Na-form coals in the fixed bed. The results indicated that the interactions between the volatiles, especially free radicals in the volatiles, and the char particles enhanced the volatilisation of Na from the char drastically. However, such radical-char interactions resulted in little volatilisation of Mg and Ca, indicating the importance of valence of the AAEM species. The degree of the volatile-char interactions was also related to the ageing of the char and the chemical form of AAEM species in the coal substrate. The volatiles interacted more strongly with the nascent char than the aged char, indicating that the AAEM species existed in the aged char in more stable forms than in the nascent char.     

PERFORMANCE OF A PRESSURIZED TWO-STAGE FLUIDIZED GASIFICATION PROCESS FOR PRODUCTION OF LOW-BTU GAS FROM COAL CHAR

A two-stage pressurized fluidized-bed gasification process has been developed to produce low-heating value gases from coal char. The reactor was 0.075 m id. and 1.4 m long, and gasification experiments were conducted under pressures up to 790 kPa and at temperatures up to 1323 K. A partition disc was used to divide the fluidized bed into two stages, using the first stage as a partial combuster and gasifier and the second stage as a gasifier. The disc was designed to control compositions of coal char particles in both stages so that the heat required for the endothermic gasification reaction in the second stage can be provided by the heat of combustion in the first

For conditions examined here, the disc with an opening ratio of 40° was found to give optimum distribution of the char particles in both stages without ash agglomeration. It was also shown that all oxygen gas was completely consumed within the first stage

The heating value of the product gas increased with the char feed rale. However, there may be an oplimum Teed ratio of char and sand-particles since the higher char feed rate causes more frequent ash agglomeration as well as less carbon conversion     

Catalytic Performance of Coal Char for the Methane Reforming Process

A new concept of combined coal gasification and methane reforming in a single reactor was proposed as an alternative path for syngas production using coal and coalbed methane. Here, the results of this process are summarized. The experimental work was carried out in a fixed‐bed reactor. Methane cracking, CO₂/steam reforming of methane over coal char, and the effects of chars made from different types of parent coal on methane conversion were examined. The catalytic effect of coal char on methane cracking and reforming increased with decreasing coalification degree. A synergistic effect was observed in that, while the coal char catalyzed the methane reforming reactions, gasification of the coal char took place simultaneously, which counter‐balanced the deposition of carbon especially for the methane‐steam‐char system.     

Effects of volatile–char interaction on the formation of HCN and NH3 during the gasification of Victorian brown coal in O2 at 500 °C

In a coal gasifier interactions between volatiles and char are significant. The partly reducing conditions in a gasifier would mean the presence of high concentration of partial oxidation products and radicals surrounding the char particles. Currently, little is known about the effects of in situ volatile–char interactions on the conversion of char-N. This study examines the effect of in situ volatile–char interactions on the formation of HCN and NH₃ during the low temperature (500 °C) gasification of Loy Yang brown coal in oxygen. Two novel reactor systems were used. The reactor configurations allowed the quantification of HCN and NH₃ from char-N gasification, volatile-N oxidation and volatile–char interactions separately. Our results indicate that volatile–char interactions can have drastic effects on coal-N conversion during gasification by providing an important source of the radicals for the formation of HCN and NH₃ from char-N during gasification in 4% or 8% O₂ at 500 °C. In the presence of radicals and O₂, N-containing structures in the nascent char can be easily broken down to give HCN and NH₃ during the gasification of the char. In the absence of O₂, some of the nascent char-N structures may stabilise into structures less favourable for the formation of HCN and NH₃ and more favourable for the formation of other N-containing species such as NO_x.     

Numerical modeling of a jetting fluidized bed gasifier and the comparison with the experimental data

A model for a jetting fluidized bed gasifier is developed, treating the grid, bubble and freeboard zones in series. Reactions including char combustion, steam gasification, CO₂ gasification and water–gas shift reaction are taken into account. The effects on model predictions of assumptions regarding the primary products of char combustion and char reactivity factor are analyzed by comparing the predictions with experimental data from a bench-scale jetting fluidized bed gasifier using different kinds of chars. Contributions of various reactions and different zones and phases to carbon conversion are analyzed.     

典型尺寸燃煤颗粒富氧燃烧特性及燃烧本征动力学研究

利用微型流化床加热速度快、温度分布均匀以及气体近平推流等优势,在直径20 mm自动控温的微型流化床反应分析仪中研究了粒度分布为1.7～3.35 mm和0.12～0.23 mm两种典型尺寸燃煤颗粒在790～900℃温度范围内的富氧燃烧行为。通过快速响应过程质谱对燃烧产生的烟气进行实时监测,成功地识别和记录了粗颗粒燃烧过程中经历的挥发分燃烧和原位新生半焦燃烧两个主要阶段。挥发分析出速度最快,然后快速燃烧,而半焦燃烧速度较慢。相比之下,细颗粒燃烧的这两个阶段具有几乎相同的速率,因而相互耦合而难以区分。根据实验结果,挥发分析出和燃烧为快速反应,煤颗粒燃烧过程速率受原位新生半焦燃烧过程控制。进一步研究了挥发分和原位新生半焦燃烧动力学行为,获得其本征动力学的活化能分别为107.2和143.9 kJ/mol。     

Fundamentals of coal topping gasification: Characterization of pyrolysis topping in a fluidized bed reactor

Coal topping gasification refers to a process that extracts the volatiles contained in coal into gas and tar rich in chemical structures in advance of gasification. The technology can be implemented in a reactor system coupling a fluidized bed pyrolyzer and a transport bed gasifier in which coal is first pyrolyzed in the fluidized bed before being forwarded into the transport bed for gasification. The present article is devoted to investigating the pyrolysis of lignite and bituminite in a fluidized bed reactor. The results showed that the highest tar yield appeared at 823 to 923 K for both coals. When coal ash from CFB boiler was used as the bed material, obvious decreases in the yields of tar and pyrolysis gas were observed. Pyrolysis in a reaction atmosphere simulating the pyrolysis gas composition of coal resulted in a higher production of tar. Under the conditions of using CFB boiler ash as the bed material and the simulated pyrolysis gas as the reaction atmosphere, the tar yields for pyrolytic topping in a fluidized bed reactor was about 11.4 wt.% for bituminite and 6.5 wt.% for lignite in dry ash-free coal base.     

CO2气氛下准东煤化学链燃烧特性研究

我国准东煤储量丰富,钠含量高。以高钠准东煤为燃料,CO₂为气化介质,铁矿石为载氧体,基于鼓泡流化床反应器开展准东煤化学链燃烧特性的实验研究,考察了煤粒径、温度、流化风速和煤焦粒径对煤及煤焦化学链燃烧过程中可燃气体逃逸规律的影响;同时研究了煤中矿物质对煤焦气化过程的影响。结果表明,在基于鼓泡流化床实施的煤化学链燃烧过程中,由于煤颗粒和载氧体床料流化特性差异大,存在离析现象;离析影响煤化学链燃烧过程中挥发分和焦炭的转化;较高流化风速可显著增强载氧体与煤/焦炭颗粒的混合,有效改善离析对可燃气体转化的影响,降低可燃气体逃逸,并加快焦炭气化速率;煤焦中的矿物质能够维持煤焦较快的气化速率。     

Factors affecting steam gasification rate of low rank coal char in a pressurized fluidized bed

A high-pressure bubbling fluidized bed reactor was used to study the steam gasification of coal char under pressure. Indonesian sub-bituminous coal char (Adaro) and Australian lignite char (Loy Yang) were gasified with steam in the reactor at temperatures below 1173 K and at total pressures ranging from 0.1 to 0.5 MPa. The steam gasification rates of the coal chars were determined by analysis of the gaseous products. Activation energies for the steam gasification of the chars were as high as about 250 kJ/mol, which suggests that the temperature dependence of the gasification was substantial. The apparent gasification rates under the study conditions were described by a Langmuir–Hinshelwood (L–H)-type equation. Analysis of the reaction kinetics on the basis of the L–H equation indicated that increasing steam pressure effectively increased the gasification rate.     

On the high‐gasification rate of Brazilian manganese ore in chemical‐looping combustion (CLC) for solid fuels

The high rate of char gasification observed when using a Brazilian manganese ore as compared to ilmenite is investigated in a batch fluidized‐bed reactor. Experiments were carried out at 970°C using petroleum coke, coal and wood char as fuel with a 50% H₂O in N₂ as fluidizing gas. A manufactured manganese oxygen carrier was also used, however, which presented a slower char conversion rate than the manganese ore. It is concluded that decrease in H₂ inhibition and oxygen release are unlikely to be the main responsible mechanisms for the ore's unexpected gasification rate. The ore was also mixed in different ratios with ilmenite and it was observed that the presence of even small amounts of ore in the bed resulted in increased gasification rate. Thus, the high‐gasification rate for the manganese ore could be due to a contribution from the impurities in the ore by catalyzing the gasification reaction. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4346–4354, 2013     

Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part VIII. Catalysis and changes in char structure during gasification in steam

The purpose of this study is to investigate the major factors influencing the Na-catalysed and non-catalysed gasification reactivity of a Victorian brown coal in steam. An acid-washed (H-form) sample and a Na-exchanged (Na-form) sample prepared from the same Loy Yang brown coal were gasified in 15% steam in a novel two-stage fluidised-bed/fixed-bed reactor. All C-containing species in the gasification product gas were converted into CO₂ that was monitored with a mass spectrometer continuously to determine the in situ gasification reactivity. While the volatile-char interactions were responsible for the volatilisation of Na when the coal was continuously fed into the reactor, the physical entrainment by gas of agglomerated Na-containing crystalline species (likely to be Na₂CO₃ or Na₂O) from char surface was the main mechanism for the loss of Na during char gasification. The Raman spectroscopy of char showed the preferential release of smaller aromatic ring system to be more significant during the non-catalysed char gasification than the Na-catalysed gasification. The dispersion of Na in char appeared to deteriorate with the enrichment of large aromatic ring systems in char, greatly affecting the char gasification reactivity. The char gasification reactivity showed a maximum with increasing conversion with the maximum to shift towards lower conversion with increasing temperature. Increasing temperature does not always lead to increases in the in situ char gasification reactivity.     

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.     

基于赤铁矿载氧体的煤化学链燃烧试验

化学链燃烧是一种具有CO₂内分离特性的燃烧方式。以赤铁矿为载氧体,在1 kW_th级串行流化床上进行了煤化学链燃烧试验。讨论了燃料反应器温度对气体产物组分的影响;比较了各反应参数对煤气化效率、煤气化产物的转化效率及碳捕集效率的影响情况,分析了煤中硫的排放问题。试验结果表明：温度由900℃升高到985℃,燃料反应器中CO体积份额逐渐增加,CO₂体积份额逐渐减小,空气反应器中CO₂浓度呈线性下降。燃料反应器温度的升高促进煤气化效率及碳捕集效率大大提高。载氧体量和系统负荷是煤气化产物转化效率的主要影响因素,载氧体量的增加和负荷的增加分别会使煤气化产物转化效率提高和下降。燃料反应器中的硫主要以SO₂形式存在于燃料反应器,随温度的升高,SO₂浓度由515×10^-6逐渐增加到562×10^-6相似文献   

Low-temperature gasification of a woody biomass under a nickel-loaded brown coal char

Catalytic gasification of a woody biomass, Japanese cypress, was investigated under a prepared nickel-loaded brown coal (LY-Ni) char in a two-stage fixed-bed reactor. The nickel-loaded brown coal was prepared by ion-exchange method with a nickel loading rate of 8.3 wt.%. Nickel species dispersed well in the brown coal, and the LY-Ni char via devolatilization at 600 °C showed a great porous property with a specific surface area of 382 m² g^− 1.The LY-Ni char was confirmed to be quite active for the Japanese cypress volatiles gasification at a relatively low-temperature range from 450 to 650 °C. For example, at 550 °C, 16.6 times hydrogen gas and 6.3 times total gases were yielded from the catalytic steam gasification of Japanese cypress volatiles under the LY-Ni char, compared with the case of non-catalyst. The biomass tar decomposition showed a dependence on catalyst temperatures. When the catalyst temperature was higher than 500 °C, Japanese cypress tar converted much efficiently, high gas yields and high carbon balances were obtained.