Influence of coal preoxidation and the relation between char structure and gasification potential

A study was carried out to ascertain the effects of coal preoxidation and carbonization conditions on the structure and relative gasification potential of a series of bituminous coal chars. Chars were prepared from two freshly mined bituminous coals and preoxidized samples derived from them. Carbonization conditions included a wide range of heating rate (0.2–10000K s^?1), temperature (1073–1273 K) and time (0.25–3600 s). Char properties were characterized in terms of analysis of char morphology, surface area, elemental composition, and gasification reactivity in air. Over the range of conditions used, preoxidation substantially reduced coal fluid behaviour and influenced macroscopic char properties (char morphology). Following slow heating (0.2 K s^?1), preoxidized coals yielded chars having higher total surface areas and higher reactivities toward gasification in air than did similar chars prepared from fresh coal. Following rapid heating (10000 K s^?1) and short residence times (0.25 s), chars prepared from preoxidized and fresh coals exhibited similar microstructural and chemical properties (surface area, $\text{C}\text{H}$ ratios, gasification rates). Carbonization time and temperature were found to be the critical parameters influencing char structure and gasification potential.     

CO2 gasification rate analysis of coal char in entrained flow coal gasifier

Coal chars of four coal types were gasified with carbon dioxide using a PDTF or TGA at high temperature and pressure. Test conditions of temperature and partial pressure of the gasifying agent were determined to simulate the conditions in air-blown or oxygen-blown entrained flow coal gasifiers. Coal chars were produced by rapid pyrolysis of pulverized bituminous coals using a DTF with a nitrogen gas flow at 1670 K. In gasification tests with the PDTF, gasification temperatures were 1670 K or below and partial pressures of carbon dioxide were 0.7 MPa or below. Carbon monoxide of 0.6 MPa or below was supplied for the gasification tests with the TGA.As a result, coal types showed a large difference in the char gasification rate with carbon dioxide, and this difference remained large without decreasing even in the high-temperature area when the gasification rate was controlled by pore diffusion the same as in entrained flow gasifiers. Inhibition of the gasification reaction by carbon monoxide was also observed. Reaction rate equations of both the nth order and Langmuir-Hinshelwood type were applied to the char gasification reaction with the random pore model and the effectiveness factor, and the applicability of these rate equations to air-blown and oxygen-blown entrained flow gasifiers evaluated. Gasification rate equations and kinetic parameters applicable to a pore diffusion zone at high temperature were obtained for each coal.     

Gasification rate analysis of coal char with a pressurized drop tube furnace

Two coal chars were gasified with carbon dioxide or steam using a Pressurized Drop Tube Furnace (PDTF) at high temperature and pressurized conditions to simulate the inside of an air-blown two-stage entrained flow coal gasifier. Chars were produced by rapid pyrolysis of pulverized coals using a DTF in a nitrogen gas flow at 1400°C. Gasification temperatures were from 1100 to 1500°C and pressures were from 0.2 to 2 MPa. As a result, the surface area of the gasified char increased rapidly with the progress of gasification up to about six times the size of initial surface area and peaked at about 40% of char gasification. These changes of surface area and reaction rate could be described with a random pore model and a gasification reaction rate equation was derived. Reaction order was 0.73 for gasification of the coal char with carbon dioxide and 0.86 for that with steam. Activation energy was 163 kJ/mol for gasification with carbon dioxide and 214 kJ/mol for that with steam. At high temperature as the reaction rate with carbon dioxide is about 0.03 s⁻¹, the reaction rate of the coal char was controlled by pore diffusion, while that of another coal char was controlled by surface reaction where reaction order was 0.49 and activation energy was 261 kJ/mol.     

Computer synthesis of char and its characterization

A mimetic method based on Monte Carlo simulation is proposed to generate a molecular model of char. This char model consists of crystalline and amorphous phases, which are heated and cooled during the simulation of the carbonization process. Resultant char shows irregular shape and interconnected pores whose properties depend on the percentage of non-organized carbon and the carbonization temperature. These chars were characterized with Monte Carlo integration techniques to obtain the pore size distribution, pore volume, solid density and surface area. These were then compared with the experimental data of two chars, longan seed derived char and coconut shell derived char. The results show that the molecular model captures the trend of the properties with carbonization temperature for both experimental chars.     

Fly ash and coal char reactivity from Thermo-gravimetric (TGA) experiments

The purpose of this research is to determine the reactivity of a sample of high carbon fly ash obtained from a circulating fluidized bed (CFB) gasification system and benchmark it against three other chars prepared at different pyrolysis temperatures in a laboratory drop tube furnace (DTF).Isothermal and non-isothermal thermo-gravimetric (TGA) experiments were used to determine sample reactivities. Structural analysis tests were carried out to establish the influence of the pore characteristics and Scanning Electron Microscope (SEM) pictures were taken for sample morphology. In-spite of high (BET) surface area and pore volume; reactivity parameters such as activation energy, kinetic rate coefficient, half life, burnout temperature and time proved the fly ash to be the least reactive. The low reactivity is associated with its carbon thermal deactivation. Non-isothermal tests also show the fly ash to be heterogeneous in composition. Of all the samples, the char prepared in the laboratory at the lowest pyrolysis temperature was the most reactive.     

随机孔模型研究煤焦O2/CO2燃烧动力学特征

在热重分析仪上对焦作无烟煤焦和云浮烟煤焦O₂/CO₂条件下燃烧特性进行研究。确定在不同温度下不同煤焦O₂/CO₂燃烧的特征。利用随机孔模型(RPM)表征两种煤焦反应速率与碳转化率的关系,同时与未反应缩核模型(Model Ⅰ)和混合模型(Model Ⅱ)的拟合结果进行比较。研究表明,在不同反应条件下,随机孔模型具有最佳的拟合效果,相关系数都在0.986以上。比较RPM、ModelⅠ和Model Ⅱ计算结果发现,焦作无烟煤焦的O₂/CO₂等温燃烧的活化能比云浮烟煤焦的高,且同一煤种燃烧反应温度越高反应速率常数越大。由于随机孔模型的结构参数ψ可以很好地表现孔结构变化对煤焦燃烧反应的影响,因此随机孔模型能更加准确地描述煤焦O₂/CO₂燃烧特征。     

Development of aromaticity in cellulosic chars

Cellulosic chars prepared at HTTs ranging up to 500°C contain aromatic structures as evidenced by the production of benzene polycarboxylic acid derivatives on permanganate oxidation. Analysis of these products indicates the concentration of the aromatic units and the degree of substitution of benzene polycarboxylic acids represents the extent of condensation or crosslinking of the structures. Further information on this subject is obtained by elemental composition of the char and the $\text{H}\text{C}$ ratio. These studies indicate a rapid weight loss and development of aromatic structures between 350 and 400°C, as the $\text{H}\text{C}$ ratio is gradually reduced from 1.5 to 0.7 and the aromatic carbon of the benzene polycarboxylic acids formed is increased to 2.5% of the carbon content of the original cellulose. Above 400°C the rate of weight loss is reduced with the formation of the “stable” char and the yield of the aromatic carbon remains constant. However, the aromatization process continues with rapid reduction in $\text{H}\text{C}$ ratio, due to the condensation and growth of the aromatic clusters as evidenced by the increased formation of the highly substituted benzene polycarboxylic acids. The presence of inorganic additives, representing flame retardants results in increased charring and enhancement of aromaticity and condensation.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.     

水热预处理对稻壳焦热电性能的影响

为了探究水热预处理对稻壳焦热电性能的影响,首先通过不同水热温度对稻壳进行改性处理,分析了其燃料特性、官能团以及热解特性。再于550℃下热解,针对热解后的稻壳焦采用工业分析、元素分析、红外光谱（FTIR）分析、X射线衍射（XRD）分析和N₂吸附脱附等方法研究改性前后稻壳焦特性及微观结构。结果表明：水热预处理后稻壳中半纤维素、碱金属和碱土金属大量减少,挥发分含量增加,并获得更多的含氧官能团。经改性后水热稻壳焦比表面积和总孔容积提高,在水热温度为150℃时达到最大比表面积335.1m²/g和最大总孔容积0.173cm³/g。用改性前后稻壳焦作为电极材料,NaCl为电解液,发现改性后稻壳焦输出电压提升明显,在50K温差下,输出电压为67.084mV,比能量为106.7mJ/g,展现了改性稻壳焦作为一种低成本多孔炭优异的热电转化性能。     

Evaporation of pyrolysis oil: Product distribution and residue char analysis

The evaporation of pyrolysis oil was studied at varying heating rates (～1–10⁶°C/min) with surrounding temperatures up to 850°C. A total product distribution (gas, vapor, and char) was measured using two atomizers with different droplet sizes. It was shown that with very high heating rates (～10⁶°C/min) the amount of char was significantly lowered (～8%, carbon basis) compared to the maximum amount, which was produced at low heating rates using a TGA (～30%, carbon basis; heating rate 1°C/min). The char formation takes place in the 100–350°C liquid temperature range due to polymerization reactions of compounds in the pyrolysis oil. All pyrolysis oil fractions (whole oil, pyrolytic lignin, glucose and aqueous rich/lean phase) showed charring behavior. The pyrolysis oil chars age when subjected to elevated temperatures (≥700°C), show similar reactivity toward combustion and steam gasification compared with chars produced during fast pyrolysis of solid biomass. However, the structure is totally different where the pyrolysis oil char is very light and fluffy. To use the produced char in conversion processes (energy or syngas production), it will have to be anchored to a carrier. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

The effect of inorganic additives on the formation,composition, and combustion of cellulosic char

At temperature above 300°C the glycosyl units of cellulose are simultaneously depolymerized to a tar and decomposed to a char by evolution of H₂O, CO, and CO₂. When the glycosyl units are depleted, a stable char is formed containing about 30% aliphatic and 70% aromatic components. The aliphatic component is formed first, but on further heating is converted to polycyclic aromatic structures. The chars formed at lower temperatures are more combustible because the aliphatic component of the char is highly pyrophoric and is oxidized almost at the same temperature at which it is formed (～360°C). The aromatic component, however, is less reactive and is oxidized at ～520°C. Consequently, the chars formed at higher temperatures are less combustible. It has been shown that (NH₄)₂HPO₄, which is a well-known flame retardant and smoldering inhibitor, lowers the pyrolysis temperature and increases the char yield by accelerating the decomposition reactions. This affects the composition of the intermediate chars but the final products have about the same composition irrespective of additives. (NH₄)₂HPO₄ also lowers the rate of oxidation of the aromatic component and the corresponding heat release. NaCl, which is an enhancer of smoldering combustion, has a slight stabilizing effect on pyrolysis of cellulose. It lowers the oxidation temperature of the aromatic component and dramatically increases its rate. The corresponding heat release is also increased due to complete oxidation to CO₂. The rate of oxidation calculated from the dynamic thermal analysis data is more than tripled by NaCl and significantly reduced by (NH₄)₂HPO₄.     

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.     

低温等离子体改性烟草焦脱除烟气中汞的实验研究

以废次烟草为原料,用盐酸溶液对800℃焦进行酸洗,然后采用低温等离子体对酸洗后的焦进行改性,研究低温等离子体改性时间对焦孔隙结构和表面化学特性的影响,以及对烟气中Hg⁰的脱除影响特性。利用氮气吸附/脱附、FTIR等方法对烟草焦改性前后的微观理化特性进行表征,在固定床上测试改性焦的脱汞率。结果表明：低温等离子体改性使烟草焦表面的孔隙结构减少,使有利于脱汞的酸性含氧官能团COOH和C=O的活性位含量随改性时间延长先增加后减小,改性作用使焦表面活性位的密度随改性时间逐渐增加。烟草焦改性后对汞的脱除率显著增加,且随改性时间的增加先增加后减小,改性5 min焦脱汞量最大,在2 h内为126.4μg/g。改性焦表面孔径偏大的微孔和中孔通道内的含氧官能团活性位对脱汞起到主要作用,而极微孔仅在吸附初期起作用,并被快速堵塞。     

Effect of carbonization temperature on the yield and porosity of char produced from palm shell

Several batches of chars were prepared from palm shell by carbonization in a flow of nitrogen using a fixed‐bed reactor. Palm shell was carbonized at temperatures of 500, 600, 700, 800 and 900 °C for 1 h to study the effects of carbonization temperature on char yield and its porosity. The prepared chars were characterized for the micropore volume using CO₂ adsorption while the meso‐ and macropore volumes were analyzed using a mercury porosimeter. The char yield was around 25% and is comparable with yields reported from other lignocellulosic materials. The results show that carbonization temperature has a significant effect on the micro‐ and mesopore volumes. However, it has negligible effect on the macropore volume. © 2001 Society of Chemical Industry     

Reaction kinetics and producer gas compositions of steam gasification of coal and biomass blend chars, part 1: Experimental investigation

Biomass and coal are important solid fuels for generation of hydrogen-rich syngas from steam gasification. In this work, experiments were performed in a bench-scale gasifier to investigate the effect of coal-to-biomass ratio and the reaction kinetics for gasification of chars of biomass, coal and coal–biomass blends. In the gasification of these chars, steam was used as the gasification agent, while nitrogen was used as a gas carrier. The gasification temperature was controlled at 850, 900 and 950 °C. Gas produced was analysed using a micro-GC from which carbon conversion rate was also determined. From the experiments, it is found that the coal and biomass chars have different gasification characteristics and the overall reaction rate decreases with an increase in the ratio of coal–to-biomass.The microstructure of the coal char and biomass char was examined using scanning electronic microscopy (SEM), and it was found that the biomass char is more amorphous, whereas the coal char has larger pore size. The former enhances the intrinsic reaction rate and the latter influences the intra particle mass transportation. The difference in mass transfer of the gasification agent into the char particles between the two fuels is dominant in the char gasification.     

Pore structure of activated carbons prepared by carbon dioxide and steam activation at different temperatures from extracted rockrose

The influence of the activation temperature on the pore structure of granular activated carbons prepared from rockrose (Cistus ladaniferus L.), extracted previously into petroleum ether, is comparatively studied. The preparation was carried out by pyrolysis of a char in nitrogen and its subsequent activation by carbon dioxide and steam (flow of water controlled to generate the same mol number per minute of water as well as carbon dioxide/nitrogen) at 700-950°C to 40% burn-off. The techniques applied to study the pore structure were: pycnometry (mercury, helium), adsorption (carbon dioxide, 298 K; nitrogen, 77 K), mercury porosimetry and scanning electron microscopy. The preparation by steam activation, especially at 700°C, yields activated carbons showing a total pore volume larger than those prepared by carbon dioxide activation. The pore structures present the greatest differences when the activations are carried out between 700 and 850°C and closer at higher temperatures. At high temperatures, the decrease of differences in pore development caused by carbon dioxide or steam is attributed to an external burn-off. The micropore structure of each activated carbon is mainly formed by wide micropores. At the lowest activation temperatures, especially at 700°C, steam develops the mesoporosity much more than carbon dioxide. At 950°C, a similar reduction of pore volume in the macropore range occurs.     

Gasification of waste biomass chars by carbon dioxide via thermogravimetry. Part I: Effect of mineral matter

A series of carbon dioxide gasification tests of waste biomass chars were performed in a thermogravimetric analysis system, at non-isothermal heating conditions. The effects of the inorganic constituents of the fuels on thermal conversion characteristics were examined. Reaction rates were determined by developing a power law model.The bulk of char gasification process occurred between 800 and 950 °C. Maximum reaction rate and conversion were exhibited by waste paper char, due to its higher surface area.Inherent alkaline and alkaline earth carbonates and sulphates acted as catalysts, by increasing the reactivity of the fuels in carbon dioxide and causing their degradation to start at lower temperatures (60-75 °C).The kinetic model fitted the experimental results accurately. Activation energy values and reaction order ranged from 180 to 370 kJ/mol and 0.4 to 0.6, respectively, among the chars, indicating a chemically controlled process.     

Influence of carbonization conditions and wood species on carbon dioxide reactivity of resultant wood char powder

Carbon dioxide reactivities of powdered samples of Acacia and Eucalyptus wood chars were measured thermogravimetrically at 900°C and the effects of carbonization conditions (temperature, heating rate and soaking time) and wood species were determined. The results showed that the reactivity decreased with increasing carbonization temperature and soaking time. Chars prepared under rapid carbonization (heating rate: 30°C min⁻¹) were found to be more reactive than the chars produced by slow carbonization (heating rate: 4°C min⁻¹). In comparison to Eucalyptus wood chars, the Acacia wood chars exhibited higher reactivity.     

Catalysis of coal char gasification by alkali metal salts

A study has been made of the gasification behaviour, in carbon dioxide and steam, of a number of coal chars doped with small amounts of alkali metal carbonates. For a given additive, the magnitude of the catalytic effect increased with the rank of the parent coal. A progressive loss in catalytic activity on thermal cycling during steam gasification was associated with reaction of the alkali salts with mineral matter in the chars. The kinetic data were consistent with catalytic mechanisms involving oxidation/reduction cycles on the char substrates.