Pore development during carbonization of coals

Changes in pore properties during carbonization at a constant heating rate and no external pressure were followed for bituminous and subbituminous coals by porosimetry, sorption and density measurements. Observations were supplemented by scanning electron microscopy and rate of volatilization measurements. All coals exhibited similar devolatilization behaviour and pore structure development, showing maximum micro and macropore volumes around 600 °C, and a partial collapse of pore structure after 800 °C. The micropore structure did not collepse in the case of non-caking coal. Pore volume maxima occur at least 100 °C above the temperature of the devolatilization rate maxima. Some interpretation is provided.     

Carbonization of coals to produce anisotropic cokes. 1. Modifying activities of some additives in the co-carbonization of low-rank coals

Using low-rank coals, the modifying activities of some petroleum, coal tar and aromatic hydrocarbon additives have been examined to find procedures for their utilization in the preparation of blast furnace coke. Petroleum pitch, especially after hydrogenation, exhibited excellent modifying activity even with non-fusible coals. In contrast, the activity of coal tar was very limited with such coals. The napththenic component, revealed by n.m.r. of the additives, appears to be important in the co-carbonization by inducing fusibility and anisotropic development in such coals. Co-carbonization to recover the dehydrogenated additives was attempted. However, there was no development of the anisotropy in the resultant coke by dissolution of the coal particles although the coal particles were firmly fixed in the matrix. Acid-refluxing treatment of non-fusible coals was found to enhance their modification susceptibility, indicating that some of the acid-soluble mineral matter is important in the thermal depolymerization or fusion process of the coal.     

Determination of organic oxygen content of coals

Fast neutron activation analysis has been used to determine organic oxygen (O_org) content of coals by subtracting the oxygen content of the mineral matter from the total oxygen content of the coals. Mineral matter was isolated by low temperature ashing in an oxygen plasma. Optimum ashing conditions produce minimal changes in chemical composition of mineral matter; these changes were taken into account when calculating the O_org content. The O_org contents of whole coals are substantially different — in some cases by as much as 47% — from the ASTM oxygen contents and those calculated on a dry, mineral matter free basis from the ultimate analysis data. Excellent agreement between the FNAA O_org contents of the whole and demineralized coals lends support to the reliability of this experimental approach.     

On the action of pyridine as a swelling agent of low-rank coals

The swelling by pyridine/benzene mixtures of low-rank coal briquette fragments is investigated, and the results are very close to those previously reported for pyridine/benzene mixtures acting on a run-of-mine coal from the same source. This is in spite of major differences in porosity between the two coals. The conclusion is that pore entry by the solvent plays no part in the swelling process.     

低阶煤低温干馏高效采油技术研究进展

低温干馏技术作为低阶煤清洁高效和科学分级利用的核心技术,已经得到国内外广泛关注。但是现有工业化应用的煤低温干馏技术存在采油率低和原料粒度要求高等问题,开发新型低温干馏高效采油技术已成为我国低阶煤利用研究的重点。本文主要从低温干馏炉的结构特征、生产原料、干馏产品、能量利用率和采油率等几个方面对国内外典型煤低温干馏炉及干馏技术进行了比较和讨论;介绍了作者课题组研究开发的低温干馏高效采油技术及其特点。分析认为,干馏炉的大型化、自动化和高效环保化;高温半焦和荒煤气热能的回收利用;粉煤资源的综合利用;干熄焦新技术;快速干馏、催化干馏技术等低温分级转化技术的研究开发是低温干馏技术今后研究开发的主要方向。     

Influence of aluminium chloride on carbonization of coal model compounds and coal derivatives

Changes in spin concentration during carbonization of coal model compounds and coal components in the presence of AlCl₃, a known carbonization catalyst, were studied with an e.s.r. spectrometer equipped with a high-temperature cavity. On addition of AlCl₃ the spin concentration during carbonization increased for compounds with three or fewer aromatic rings and decreased for those with four or more. Only the spin concentration of the quinoline-soluble component of a low-reflectance coal increased during carbonization in the presence of AlCl₃. These phenomena are discussed in terms of molecular orbital theory.     

Model for drying during fluidized-bed combustion of wet low-rank coals

An unsteady state heat conduction model with a convective boundary condition is proposed for the drying of low-rank, high-porosity coals, such as lignites, during fluidized-bed combustion. The drying front is assumed to be the receding surface of a wet core. The solution technique for this moving boundary problem is based on the heat balance integral approach with immobilization of the moving boundary by a change in space variable. The governing cubic equation describing the drying curve in dimensionless form may be solved easily by the Newton—Raphson method. The model predictions are compared with experimental data for Mississippi lignite with excellent agreement. A correlation for estimation of total drying time is proposed. The temperature profiles obtained may be used for the study of the coupled drying and devolatilization in fluidized-bed combustors. The profiles could also be of importance in the study of formation of fissures/cracks in lignites subjected to intense heating conditions encountered during fluidized-bed combustion.     

Comments on the reactivity of low-rank coals in liquefaction

This communication discusses the subject of the relative reactivities of low-rank and bituminous coals in liquefaction. Accounts given by several researchers have provided seemingly contradictory results. An explanation is presented to reconcile these opposing views.     

Fate of aliphatic groups in low-rank coals during extraction and pyrolysis processes

Information on the nature of aliphatic groups in some bituminous coals and lignites was obtained by determining their fate during extraction and pyrolysis processes of differing severity. Aromatics (neutral oils) and asphaltenes from supercritical gas and hydrogen-donor solvent extracts and from pyrolysis and hydropyrolysis tars have been characterized by an n.m.r.-based structural analysis method which identifies hydroaromatic, methyl and long alkyl (?C₈) groups. The results indicate that methyl and other alkyls account for about half of the aliphatic carbon, long alkyl chains being the major aliphatic group in the lignites. There is evidence to suggest that some of the long alkyl chains are joined to aromatic structures. Hydroaromatic groups are small consisting of only 1–2 rings and account for less of the aliphatic carbon in bituminous coals than previously thought. Their concentrations and those of long alkyl chains in the aromatics and asphaltenes generally decrease with increasing process severity.     

Carbonization of coals to produce anisotropic cokes.: 4. Improving co-carbonization behaviour of bituminous and subbituminous coals with pitch by pretreatment coals to remove cations

Several de-ashing pretreatments of selected coals have been examined to establish simple and effective procedures to improve, in terms of anisotropic development, the co-carbonization behaviour of the coals with pitches. Refluxing pretreatments of the coals in 1N HCI containing methanol and in boiling water containing EDTA-2Na (EDTA-2Na/coal = 7/100 byweight) improve the co-carbonization behaviour of Witbank, Miller, Taiheiyo and Wandoan coals, all of which, in their original, untreated form, are modified in terms of anisotropic development only very slightly in co-carbonizations with A240 petroleum pitch. Pretreatment of coals of very low rank appears to be ineffective in co-carbonizations with A240; however, co-carbonization with hydrogenated A240 shows that the pretreatments are effective. Analyses and FT-i.r. spectroscopy of mineral matter suggest that improved behaviour due to the pretreatment is related to the removal of divalent cations and to the modification of the oxygen functionality of the coals.     

Determination of carboxyl groups in low-rank coals

The determination of carboxyl groups in low-rank coals by exchange with barium chloride-triethanolamine reagent is re-examined. The difference in carboxyl contents calculated from the barium content of the exchanged coal, and the amount of acid used to extract the barium, is discussed. Reliable carboxyl contents are obtained providing the latter procedure is used.     

Influence of air oxidation on the pressure exerted by coking coals during carbonization

The effects of air oxidation of three Spanish coals on the pressure exerted during carbonization have been studied. Coals were oxidized by air in an oven at 120 and 140 °C. The extent of oxidation was assessed by the Audibert-Arnu dilatometer test. Coal samples oxidized at different levels were subjected to the Koppers-lncar laboratory coking pressure test. The results obtained indicated that for coals classified as ‘dangerous’ the ‘danger’ increased and reached a maximum at a certain level of oxidation, after which it decreased sharply. This behaviour did not occur with coals classified as safe.     

Carbonization reactions of inertinite macerals in Australian coals

Widespread disagreement about the degree of reactivity of the inertinite group of macerais is related to variations in experimental conditions of assessment and failure to appreciate technological modifications imposed on similar macerals by dissimilar source materials and depositional conditions. This has resulted in the constant under-estimation of the coking potential of post-Carboniferous inertinite-rich coals by predictive methods developed for vitrinite-rich Carboniferous coals. Coking tests up to 1000 °C have been carried out on 20 coals of different rank in such a manner that coked portions of the samples could be correlated with their uncoked equivalents. It has been found that an inverse relationship exists between the level of precarbonization reflectance (PCR) of inertinite and the reflectance and bireflectance of its coke. The increase in the latter parameter is non-linear and involves a sudden jump which is taken as the boundary between reactive (high bireflectance) and non-reactive (low bireflectance) inertinite. In relation to coal rank a reactivity field for inertinite has been delineated which can be subdivided into two areas of high and moderate reactivity, respectively. On the whole, the proportion of reactive inertinite is larger than allowed for in most petrography-based coke stability calculations.     

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     

炭化过程对聚丙烯腈基活性中空炭纤维性能的影响

聚丙烯腈(PAN)中空纤维在空气中250℃预氧化2 h后,在氮气气氛中炭化,得到PAN基中空炭纤维(PAN-CHF),再在二氧化碳气氛中活化,得到PAN基活性中空炭纤维(PAN-ACHF)。考察了炭化温度和炭化时间对PAN-CHF的收缩率、PAN-ACHF的收缩率、活化收率、比表面积和吸附性能的影响。结果表明:炭化温度为1 000℃时,PAN-CHF和PAN-ACHF的收缩率相同;炭化温度为900℃时,PAN-ACHF的比表面积最大,吸附性能最好,炭化时间对PAN-CHF和PAN-ACHF的收缩率影响不大,但活化收率随炭化时间延长呈上升趋势,比表面积先增后降,炭化时间为60 min时达到最大,其吸附量最大。     

Some aspects of changes in the macromolecular structure of coals in relation to thermoplastic properties

The development of coal thermoplasticity during the primary devolatilization region is critical in determining coke structures. The solvent swelling technique was used to study the changes in macromolecular structure of four coals of different rank (902 to 203 in the British Coal classification scheme) during carbonization to temperatures up to 600°C. The results were compared with the thermoplastic characteristics of the coals. The dilatometric and gas permeability properties are discussed in terms of changes in macromolecular structure. The study of the macromolecular structure provides new insight into the development of thermoplasticity and coke structure.     

Oxygen removal during the direct liquefaction of low-rank materials: Stoichiometric considerations

Two mechanisms of oxygen removal which may occur during the conversion of low-rank materials into transport fuels are compared. Alternative reaction pathways are assumed and the stoichiometries of these are used as the basis of the analysis. Conditions at which the two deoxygenation routes lead to the same profitability of process are determined. Similarly, conditions at which lower-rank materials can compete with higher-rank materials are defined. Comparison with coal liquefaction data suggests that, at the same energy price, lower-rank feedstock can compete with higher-rank material in self-contained processes where the processing costs, exclusive of the costs of reducing gas, are similar on a feed energy basis.     

Pore entry effects in the solvent-induced swelling of low-rank coals

The swelling of a low-rank coal under the influence of various solvents is examined and results compared with those for a similar coal in briquetted from. Results are interpreted in terms of the effects of briquetting on pore structure.     

煤焦油渣炭化过程中孔结构及表面分形特征

利用煤气化焦油渣为原料进行活性炭制备实验研究,对炭化过程焦油渣孔结构和表面特征进行研究,采用N₂吸附/脱附等温实验和表面分形理论研究炭化对焦油渣孔结构和表面特征的影响。结果表明：炭化物的吸附等温线倾向于表征微孔吸附特征的Ⅰ类吸附等温线;炭化物中具有发达的微孔结构、过渡孔结构和极不发达的大孔结构;随着温度和升温速率的提高,微孔结构先增加后又逐渐发展为过渡孔和大孔;对炭化物表面的分形特征进行研究发现,表面分形维数与BET比表面积、总孔容、平均孔径不存在直接关系,但是与微孔面积占比和微孔容积占比存在较好的一致性;焦油渣在炭化处理过程中随着温度的升高和升温速率加快,经历了“立体发展-逐渐衰落”的过程。当炭化终温850℃、升温速率20℃/min时,可以得到最优的活化前体。     

过滤式厌氧折流反应器处理焦化废水研究

试验运用过滤式厌氧折流反应器 (FABR)对焦化废水进行处理。结果表明 :采用颗粒活性炭作为挂膜载体时 ,小粒径 (0 .4 5～ 0 .90mm)优于大粒径 (0 .90～ 3.0 0mm) ,利于FABR快速挂膜启动 ;进水COD质量浓度中等 (16 0 0～ 2 5 0 0mg/L) ,COD容积负荷小于 2kg/ (m3 ·d) ,水力停留时间大于 4 0h ,温度在 34～ 38℃范围内 ,pH为 7～ 7.6时 ,COD和NH3 -N去除率均可达 70 %。厌氧处理后可提高焦化废水的可生化性 ,再经好氧处理 ,COD和NH3 -N去除率均可达 85 %以上