Production of isotropic coke by thermocracking of the anthracene fraction of coal tar

The properties of coke obtained by heat treatment of the anthracene fraction of coal tar under pressure (by thermocracking) are investigated. Pressures up to 5 MPa are used; the temperature is 500 or 550°C. For comparison, pitch coke is obtained from oxidized pitch with softening temperatures of 166.2 and 190.2°C. The coke yield from thermocracking is 70–75%. The following properties of the coke are determined: the actual density, the ash content, the yield of volatiles, the optical microstructure, the elementary composition, the change in volume on heating to 2400°C, the impurity composition, and the X-ray structural characteristics. High temperatures (at least 550°C) and heating rate of the anthracene fraction facilitate the formation of a large quantity of active radicals, which instantaneously form the three-dimensional coke structure, preventing the growth and coalescence of mesophase particles; isotropic coke is formed, with a microstructure score of 2.2. At 500°C, anisotropic coke is formed, with a microstructure score of 4.3. Despite the high softening temperature and the content of the α1 fraction, the high-temperature pitch does not form isotropic coke on carbonization. The macrostructure of the coke obtained by thermocracking is monolithic, with fine pores. The thermocracking conditions (temperature, pressure, presence of H₂) facilitate partial destruction and hydrogenation of the heterocyclic compounds. As a result, the coke has a reduced N, S, and O content. For pitch coke, the nitrogen content is 20–40% higher. The lack of ash in the anthracene fraction of coal tar results in ash- and metal-free coke. The coke obtained by thermocracking also has satisfactory X-ray structural characteristics and undergoes practically no expansion on graphitization, in contrast to pitch coke. In view of the technological convenience (absence of liquid products, high coke yield) and the quality of the coke, the production of isotropic coke by thermocracking may be regarded as a promising means of supplying the raw material used to produce artificial graphite.     

Physico-chemical interactions of coal and pitch during co-carbonization

Co-carbonization of non-coking coals and pitch materials has been followed by optical microscopy and thermogravimetry. The results obtained at a heating rate ? 5 K min^?1, clearly indicate a strong correlation between the thermogravimetric behaviour of the blend and the development of anisotropic texture in the resultant coke. For non-interacting systems, i.e. no enhancement of the anisotropic texture, the instantaneous rates of weight losses during carbonization of each component in the blend are almost additive. In contrast, for interacting systems, the thermogravimetric behaviour of the blend differs widely from the one obtained by adding the rates of weight losses of each component taken separately. The improvement of anisotropy of a coke by adding pitch to the initial coal results from a chemical stabilization of the system by pitch in the temperature range where, in the absence of pitch cross-links are formed which hinder the subsequent formation of large organized aromatic units.     

Carbonization of coals into anisotropic cokes: 8. Carbonization of a canadian weathered coal into anisotropic coke

The carbonization properties of a weathered high rank bituminous coal were compared with those of the non-weathered coal. The weathering decreased the fusibility of the coal to leave more basic anisotropy and to diminish the size of the majority of the anisotropy in the resulting coke. On the other hand, more domain and flow domain textures developed. Co-carbonization with a petroleum pitch additive (Ashland A240) was found effective in enhancing the fusibility of the coal and anisotropic development in the coke. Formed coking of the weathered coal by means of copreheat-treatment with the additive, provided an anisotropic, dense and strong coke of uniform size. For the weathered coal, the optimum copreheat-treatment was shorter than that using the non-weathered coal indicating high coking reactivity of the weathered coal. The transferable hydrogens from the additive are rapidly consumed by the oxygen containing groups of the weathered coal.     

Carbonization and liquid crystal (mesophase) development. 14. Co-carbonization of coals with A240 Ashland petroleum pitch: effects of conditions of carbonization upon optical textures of resultant cokes

This study examines the effect of pitch concentration, rate of heating, soak temperature and time of soak upon the optical texture of cokes prepared from the co-carbonizations of a coal (Oxcroft-Clowne, NCB Rank 802) and three vitrains of NCB Rank 204, 801, 902 with Ashland A240 petroleum pitch. Using the coal (Rank 802) with 10 wt % and 25 wt % additions of pitch caused progressive penetration of the pitch into the coal with a resultant development of a mozaic anisotropy in the coke to replace partially the original coke isotropy. With 50 wt % addition of pitch almost all of the coal particles, 600 to 1100 μm in size, were modified during carbonization. Some pitch coke was formed. For the coal and three vitrains with increasing rates of co-carbonization from 0.5–10 K min^?1 to 1200 K, using 25 wt % of A240 pitch, resultant cokes showed progressively increased extents of modification. For the two vitrains (Rank 801, 902) soaking at temperatures of 650–690 K caused a decrease in the extent of modification of isotropic coke when compared with the coke of HTT 1200 K. Evidently fast heating rates create the conditions of fluidity necessary for the pitch to modify the coal leading to growth of mesophase and anisotropic coke.     

高钠煤灰烧结特性研究进展

中国新疆准东煤具有储量巨大、开采成本低、挥发分高、硫含量低等特点,是优质的动力用煤。但准东煤钠含量高,燃烧利用时易在受热面上形成烧结性积灰,产生严重的结渣,极大限制了高钠煤的开发利用。因此,要实现高钠煤的清洁高效利用,需充分认识高钠煤灰的烧结特性。总结了高钠煤积灰结渣机理,概述了高钠煤灰烧结机制,探讨了二者之间的内在关联。高钠煤在燃烧过程中,煤中碱金属(主要为钠)释放并以Na_2SO_4、NaCl及Na的形式存在于烟气中,与受热面接触并于其上冷凝形成黏性内白层,内白层捕获飞灰颗粒后反应生成低熔点化合物,其烧结温度降低,使锅炉受热面上发生沾污增强型的"沾污烧结"过程。高钠煤灰的烧结过程包含固相烧结、液相烧结和气相烧结3种方式,对煤灰烧结过程的影响因素包括反应温度、化学组成、煤灰粒径、反应气氛、添加剂种类、锅炉设计和锅炉运行工况等。其中添加剂按氧化物种类可分为碱性氧化物和酸性氧化物,一般情况下碱性氧化物可以降低煤灰烧结温度,酸性氧化物可提高煤灰烧结温度。未来对于提高高钠煤灰烧结温度的研究方向可从新型添加剂出发,找到既能固定烟气中的钠,又能与灰渣中的低熔点含钠矿物质反应生成高熔点化合物的单一或混合成分的添加剂。同时,关于钠蒸气对积灰结渣在微观层面上的动态特性的影响机制也需进一步研究。概述了煤灰烧结温度的测量方法,热导率分析法、压力测量法、热机械分析法、筛分法和压降法,其中压降法是目前为止测量烧结温度较为准确的方法。介绍了上海理工大学碳基燃料洁净转化实验室在高钠煤灰烧结特性方面的研究方向,以期为解决燃用高钠煤锅炉积灰结渣问题提供参考。     

Influence of additives of various origins on thermoplastic properties of coal

Two coking coals of different rank were chosen in order to assess the influence of various additives on their thermoplastic properties. Six additives of different origin and characteristics were selected: two non-coking coals, together with a commercial coal tar pitch, a residue from the bottom of the benzol distillation tower and two residues from the tyre recycling industry. The effect of the additives on coal thermoplastic properties was assessed by means of the Gieseler test. The additives were pyrolyzed to a final temperature of 550 °C and the tar characterized by means of Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC). The influence of the additives on coal thermoplasticity is related to the volatile matter content of the additive, its evolution profile with temperature and the composition of the tar obtained during the pyrolysis of the additives.     

Influence of carbonization conditions on the development of different types of optical anisotropy in cokes

The vitrain components of a series of coal samples were carbonized at temperatures from 400 to 1000°C at different rates of heating ranging from 0.5 to 10°K/min and utilizing soaking times up to 24 hr. Polished specimens prepared from the carbonized products were examined microscopically under polarized light in order to determine the proportions of the various types of optical anisotropy present in them. The variations in heating rate and soaking time were found to exert little significant influence on the anisotropy developed in high-temperature cokes. But in semicokes produced at carbonization temperatures within the plastic range the influence of the carbonization conditions was much more pronounced with the effects being inter-related. Decreasing the heating rate or increasing the soaking time led to the optical anisotropy generally becoming detectable at lower carbonization temperatures. Fast heating rates caused an increase in the rate of transformation of the fine-grain mosaic anisotropy into coarser-grained types of anisotropy and increased soaking time led to enhanced anisotropic development in the semicokes produced at temperatures within the plastic range. The type of anisotropy developed in cokes is closely related to the release of volatile matter and the plasticity developed during carbonization and the conclusion is drawn that the balance between these factors controls the extent of the anisotropic development.     

Characteristics and carbonization behaviors of coal extracts

N-methyl pyrrolidone (NMP) raw coal extract (EXT), hydrogenated coal extract (HEXT) and the blend of EXT and HEXT in NMP (BLD), from two bituminous coals, were studied. The extracts were carbonized in both tube-bomb and a temperature programmable furnace. Elemental analysis, FTIR spectroscopy and optical microscopy techniques were employed to characterize the extracts and the carbonization residues. It was found that the extracts resembled petroleum-derived pitches in the hydrogen content and (C/H)_atomic ratio. Higher oxygen and nitrogen contents differentiated the coal extracts from commercial petroleum pitch. More carbon and hydrogen, and lesser oxygen and sulfur differentiated HEXT from EXT. The ratios of integrated IR band intensity for aromatic and aliphatic CH stretching indicate that the relative content of aliphatic hydrogen in EXT is higher than in HEXT. HEXT contains comparatively more aromatic hydrogen, a feature necessary for thermal stability and fluidity during carbonization. BLD materials are at a place somewhere in between. Kinetic modeling of the aliphatic hydrogen change during carbonization reveals that EXT has high carbonization rate and low apparent activation energy. This can be related to the optical texture size of carbonization residues. The residues made from EXTs exhibited fine mosaic optical texture and limited mesophase development. HEXTs were readily converted into highly anisotropic coke. BLDs produced carbonization residues with intermediate properties. Extracts with similar activation energies produced similar residues in the same coal series. The degree or extent of anisotropy displayed by the carbonization residues was found to be dependent on the relative distribution of aromatic and aliphatic hydrogen.     

添加剂对催化气化工艺中煤灰结渣性及气化性能影响研究

煤催化气化工艺中碱金属催化剂的引入加剧了气化炉的结渣，直接影响了流化床气化炉的正常操作。煤灰的烧结特性是流化床气化炉结渣的主要影响因素之一。通过自制的压差法烧结温度测定实验装置，并结合XRD 等分析表征及Factsage热力学软件模拟计算，考察了不同添加剂对煤灰烧结特性及气化性能的影响，并从矿物学角度探讨了添加剂对煤灰结渣特性及气化工艺的影响。结果表明，添加硅铝系添加剂可提高煤灰的烧结温度；相比硅系添加剂，添加高铝系添加剂对改善煤灰的烧结温度效果更明显；高铝系添加剂可作为一种高效的阻熔剂，但因在气化过程中容易同催化剂反应，导致催化剂催化性能降低，对煤的气化活性及催化剂回收率产生不利影响；添加氧化钙添加剂，煤的灰熔温度及烧结温度均增加，随氧化钙含量增加，灰熔点及烧结温度均升高，且对气化活性及催化剂回收率有良性作用；氧化钙可作为改善煤种结渣性的添加剂用于催化气化工艺中，需根据煤种性质及工艺特点确定适宜的添加量。     

The effect of coal blend fluidity on the properties of coke

The effect of maximum fluidity of coal blends on coke quality was investigated using high fluidity coals and pitch to increase the fluidity of the blends. The results show that high fluidity of the blends could improve the growth of anisotropic carbon in coke. It also improves the coke M₃₀, but this is restricted when using high fluidity coals as additives. There is no significant improvement of the M₁₀ by increasing the fluidity. The reactivity, however, could be reduced to lower than the expected value by increasing the coal blend fluidity.     

Carbonization and liquid-crystal (mesophase) development. 10. The co-carbonization of coals with solvent-refined coals and coal extracts

Coals (NCB rank 102 to 902) were co-carbonized with solvent-refined coals and coal extracts, mixing ratio of 7:3, to 873 K, heating at 10 K min^?1 with a soak period of 1 h. Resultant cokes were examined in polished section using reflected polarized-light microscopy and optical textures were recorded photographically. These optical textures were compared to assess the ability of the additive pitch to modify both the size and extent of optical texture of resultant cokes. The objective of the study is to provide a fundamental understanding of the use of pitch materials in co-carbonizations of lower-rank coals to make metallurgical coke. A Gulf SRC was able to modify the optical texture of cokes from all coals except the anthracite. Soluble fractions of this Gulf SRC were less effective than the parent SRC. A coal extract (NCB D112) modified coke optical texture, the extent being enhanced as the rank of coal being extracted was increased. Hydrogenation of the coal extract increased the penetration of the pitch into the coal particles but simultaneously reduced the size of the optical texture relative to the non-hydrogenated pitch. This indicates a positive interaction of pitch with coal in the co-carbonization process. The optical texture of the cokes from the hydrogenated coal extract in single carbonizations was larger than that from the non-hydrogenated material. Mechanisms explaining these effects are briefly described.     

Carbon foam derived from pitches modified with mineral acids by a low pressure foaming process

Carbon foams with an anisotropic texture and high mechanical strength were produced using precursors obtained after thermo-oxidation treatment of commercial coal-tar pitch with H₂SO₄ and HNO₃. The investigations of the relation between the properties of the precursor and the structure of obtained foam indicate, that the composition and softening point of the pitch precursor significantly affect the foaming process, foam structure and foam mechanical strength. The composition and properties of the modified pitches allow foam formation at relatively low pressure and fast heating rate during the foaming process without a stabilization treatment. The foaming process of pitch-based carbon foams, pre-treatment of the precursors, and the properties of resultant foams are discussed in this paper.     

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.     

Co-carbonization of hard coals and coal extracts 2. The co-carbonization of medium- and high-rank coals with extracts

Studies on the influence of anthracene coal extracts on the carbonization process of medium- and high-rank coals were undertaken. Extracts from flame coal (Int. Class. 900) and gas-coking coal (Int. Class. 632) were used as additives. The blends prepared from the examined coals and the extracts exhibited better coking properties than the parent coals. The addition of extract to the coals gave an increase in the microstrength of the resultant cokes. The effects of co-carbonization of coking coals with extracts were increases in the size of the optical texture as well as in the degree of structural ordering of cokes. In the co-carbonization of semicoking coal with addition of coal extracts, a reduction in the size of the anisotropic units and a decrease in the crystallite height of cokes were observed. No modification of the basic anisotropy of coke from anthracite by coal extract was observed. With increasing extract content in anthracite/extract blends there was an increase in the degree of structural ordering of co-carbonization products. Extract addition was unable to modify the behaviour of fusinite. Based on the results of investigation of the influence of coal extracts on the carbonization of different-rank coals, a division of coals according to the modification of the optical texture of coke is given.     

煤沥青球的氧化不熔化过程特性

氧化不熔化过程是煤沥青基球状活性炭制备中的核心工艺,对其过程特性和动力学机理的认识是实现氧化过程工艺优化的关键。本文以煤沥青萃取球为原料,通过实验研究,重点探讨了粒径范围、升温速率和氧化温度对其氧化不熔化过程的影响,并确定氧化动力学参数及其反应机理函数。结果表明：氧化不熔化过程可分为轻组分热解、初步氧化、氧化增重和恒温氧化失重4个阶段。煤沥青球经过氧化不熔化后,C、H含量减少,O含量增加,表面光滑平整。减小粒径并选取合适的升温速率（0.25～0.5℃·min^-1）以及氧化温度（275～325℃）,更有利于氧化不熔化快速稳定地进行。粒径范围为0.3～0.6 mm的煤沥青球在升温速率为0.5℃·min^-1、氧化温度为300℃的条件下活化能最小,各个阶段的值分别为83.34、293.19、302.25和357.05 kJ·mol^-1。     

Some aspects of the role of coal thermoplasticity and coke structure in coal gasification. 1. The effect of rank on high pressure dilatometry parameters

The thermoplastic properties of ten coals of rank 301a to 902 in the NCB Classification Scheme have been investigated using a high pressure dilatometer. The results show that the swelling behaviour of a coal at high pressure cannot be accurately predicted from a single measurement under standard conditions (3°C min^?1, 0.1 MPa). The data also clearly show that the large differences in dilatation observed under standard conditions for the range of coals investigated are much reduced at high pressures, e.g. > 4 MPa. The trends in dilatometry parameters in relation to rank and pressure are discussed in detail. The relative order of coals based on dilatation may change with increase in pressure and this mainly occurs in the pressure range up to 2.5 MPa. The results suggest that the characterization of coals for high pressure gasifiers should include measurements under simulated gasifier conditions rather than standard tests at atmospheric pressure.     

Rapid devolatilization and hydrogasification of bituminous coal

Rapid devolatilization and hydrogasification of a Pittsburgh Seam bituminous coal were studied and an appropriate coal conversion (weight loss) model was developed that accounts for thermal decomposition of the coal, secondary char-forming reactions of volatiles, and homogeneous and heterogeneous reactions involving hydrogen. Approximately monolayer samples of coal particles supported on wire mesh heating elements were electrically heated in hydrogen, helium, and mixtures thereof. Coal weight loss (volatiles yield) was measured as a function of residence time (0–20 s), heating rate (65–10000 °C/s), final temperature (400–1100 °C), total pressure (0.0001–7 MPa), hydrogen partial pressure (0–7 MPa), and particle size (70–1000 μm). Volatiles yield under these conditions increases significantly with decreasing pressure, decreasing particle size, increasing hydrogen partial pressure and increasing final temperature, but only slightly with increasing heating rate. The data support the view that coal conversion under these conditions involves numerous parallel thermal decomposition reactions forming primary volatiles and initiating a sequence of secondary reactions leading to char. Intermediates in this char-forming sequence can escape as tar if residence time in the presence of hot coal surfaces is sufficiently short (e.g. low pressures and small particles well dispersed). Hydrogen at sufficiently high partial pressure can interrupt the char-forming sequence thereby increasing volatile yield. Rate of total product generation is largely controlled by coal pyrolysis while competition between mass transfer, secondary reactions, and rapid hydrogenation affects only the relative proportions of volatile and solid products formed.     

Carbonization of coal blends: mesophase formation and coke properties

Laboratory investigations of strength of cokes from blends of coals incorporating pitch were supported by 7 kg trials. The stronger cokes showed a greater interaction between coal and pitch to produce an interface component of anisotropic mozaics which is relatively resistant to crack propagation. The process whereby coal is transformed into coke includes the formation of a fluid zone in which develop nematic liquid crystals and anisotropic carbon which is an essential component of metallurgical coke. Strength, thermal and oxidation resistance of coke can be discussed in terms of the size and shape of the anisotropic carbon which constitutes the optical texture of pore-wall material of coke. Coals of different rank form cokes with different optical textures. Blending procedures of non-caking, caking and coking coals involve the interactions of components of the blend to form mesophase and optical texture. Petroleum pitches used as additives are effective in modifying the carbonization process because of an ability to participate in hydrogen transfer reactions.     

煤粉高压着火特性及影响因素

高压气化炉内煤粉的着火特性对煤粉烧嘴和气化室的设计与运行调控具有重要意义。笔者采用加压热重分析法对3个煤样的着火特性进行研究,根据升温过程中的能量守恒原理和谢苗诺夫着火理论提出了一种新的处理PTG曲线求取着火温度的拐点法,并与传统经验切线法进行对比;讨论了压力、氧气体积分数、升温速率、挥发分和颗粒粒径对着火温度的影响。研究结果表明,煤粉着火温度区间为从初始着火温度(Ti)到极限着火温度(Tig),环境换热条件所决定的切点位置是唯一定解条件,高温工业炉高加热速率对应的为极限着火温度;与常压条件下相比,加压下固定床煤粉的着火为异相着火,着火温度随挥发分的增加而略有增加;在0.1~1.0 MPa和3~5 MPa的压力范围内,随压力的升高,着火温度下降,且比常压下低很多,虽然在1~3 MPa的着火温度略有增加;氧气体积分数对着火温度的影响规律与常压的类似,随氧气体积分数的增加,着火温度降低;虽然加压条件下煤粉的快速反应,拐点法与切线法得到的着火温度相近,但切线法无法响应环境条件的变化,且常压下,经验的切线法无法给出令人满意的结果。     

Preparation of active carbons from coal Part I. Oxidation of coal

The oxidation of coals of different rank, origin and particle size has been studied at temperatures between 423 and 543 K and for time intervals between 6 h and 42 days. The chemical composition of the oxidised coal depends upon the coal rank, its particle size and the degree of oxidation as determined by the temperature and the time of oxidation. At higher degrees of oxidation, whether at higher temperatures for shorter time intervals or at lower temperatures for longer time intervals, the oxidised coal tends to approach similar chemical compositions. The weight of coal also changes on oxidation, the increase or decrease in weight depending upon the rank and the oxidation conditions. The rate and extent of oxidation decrease with increase in particle size because the larger particles slow down the diffusion of oxygen into the coal particles. The oxidation can eliminate completely the plastic properties of bituminous coal which inhibit the formation of anisotropic structures and enhance the development of a primary pore structure. The helium density increases with the degree of oxidation but the mercury density initially increases and then decreases. A minimum in the mercury density is obtained when the carbon content of the oxidised coal is around 85–90%. The oxidation significantly enhances the porosity and the surface area, the extent of increase depending upon the nature of the coal and the degree of oxidation. The changes in chemical composition, porosity and surface area with the degree of oxidation indicate that the oxidation of coal involves two different mechanisms, one operating at lower temperatures and the other at higher temperatures.