炼焦煤煤化度表征的研究

对8组挥发分相同或接近的不同矿点炼焦煤进行了实验,分别测定了8组煤的煤岩组分和镜质组平均最大反射率、软化起始温度,通过对比分析可知:具有相同或相近挥发分的煤,由于煤岩组分的差异,镜质组平均最大反射率的差值达到0.03%~0.24%;并不是惰质组含量的差值越大,镜质组平均最大反射率的差值就越大,惰质组含量差值8%~9%的炼焦煤,镜质组平均最大反射率的差值几乎一致。建议炼焦企业尽可能通过镜质组平均最大反射率来认识炼焦煤的煤化程度,从而提高煤质技术理论水平。     

Carbonization and liquid-crystal (mesophase) development. Part 3. Co-carbonization of aromatic and heterocyclic compounds containing oxygen, nitrogen and sulphur

A detailed investigation is reported of the effects upon size and shape of anisotropic mesophase structures in resultant semi-cokes of co-carbonizing eighteen oxygen-, nitrogen- or sulphur-containing compounds with fluorene, carbazole and acenaphthylene. Carbonizations were carried out under pressures of 130 to 320 MN m⁻² to a maximum heat-treatment temperature of 873 K, the mesophases being examined by optical and scanning electron microscopy. Additions of phthalimide, phthalic anhydride or pyromellitic dianhydride to fluorene and carbazole caused development of anisotropic carbon where none was formed on carbonization of the single compounds, or enhanced existing mesophase growth processes. Improvements in mesophase growth result in improved graphitizability of the semi-coke. Of the oxygen-containing compounds, the polycyclics with quinone groupings, or monocyclic molecules with several functional oxygen groupings, assist the growth of anisotropy. Phenol severely retards mesophase growth. Reasons are advanced which incorporate mechanisms of liquid-crystal formation. The implication for coal carbonization is that as the oxygen content in coals, on coalification, becomes increasingly attached to aromatic systems, then the oxygen in prime coking coals may actually enhance the growth of the mesophase during its carbonization. Nitrogen- and sulphur-containing compounds on co-carbonization with acenaphthylene at nitrogen or sulphur contents greater than 3% by weight may cause deterioration of mesophase growth. Such compounds do not significantly affect the carbonization of prime coking coals, but may contribute to the smallness of anisotropic structures in the carbons from coals of lower rank.     

Investigation into the fate of mercury in bituminous coal during mild pyrolysis

Two high-volatile bituminous coal (Lower Freeport #6A and Pittsburgh #8), used primarily for electricity production, were tested to determine the fate of their mercury content during mild pyrolysis. Mono-sized samples of the well characterized coals were tested under nitrogen in a horizontal tube furnace at different residence times at different temperatures throughout the range 275–600°C. The resulting char was analyzed for mercury, and compared to the original parent coal concentration. The percent Hg removal was found to be a function of both residence time and temperature. The data for both coals have shown two distinct regimes; a low temperature chemical evolution mechanism which follows an Arrhenius form (apparent activation energies for the Lower Freeport #6A and the Pittsburgh #8 coals are 25.6±1.5 and 21.7±1.9 kcal/mol respectively), and a higher temperature regime where the Hg evolution dramatically decreases. This can be attributed to the changing structure of the coal at these higher temperatures. The results of bomb calorimetry analysis performed on the Lower Freeport #6A coal samples verify that the overall heating value of the coal is essentially unaffected by mild pyrolysis at temperatures lower than 400°C.     

Interactions between coking coals and plastics during co-pyrolysis☆

Blends of three Australian coking coals and polypropylene, polystyrene, polyacrylonitrile and polyphenylene sulfide were prepared and the extent to which the blends fused on heating was monitored using proton magnetic resonance thermal analysis in order to identify interactions between them that could affect their fluidity. Different plastics had different effects. Polystyrene strongly reduced the fluidity of all of the coals, confirming previous findings. Polypropylene did not affect the fluidity of the two coking coals of lower rank. Polyphenylene sulfide reduced the fluidity of the coals at temperatures near the solidification temperature of the coals, and polyacrylonitrile appeared to increase the fluidity of the coals at temperatures near the softening temperature of the coals. The very different effects different plastics have on coal fluidity show that the interaction between plastics and coals must be carefully examined before plastics are added to coking coal blends.     

Change of pore properties during carbonization of coking coal

Porosimetry, sorption and density measurements are reported on two caking bituminous coals, West Virginia Jewel No. 2 medium volatile and a Pennsylvania Pittsburgh seam high volatile C, for final carbonization temperatures between 400 and 1000°C. Samples were not confined and heating rates of 3 and 8.2°/min were employed. The medium volatile samples exhibit pronounced maxima in pore volume, pore surface area and porosity between 600 and 800°C. These temperatures are considerably greater than the characteristic temperature and the temperature at which maximum dilation occurs. The high volatile C coal does not exhibit well defined maxima. Results are interpreted in terms of pore development mechanisms. A mathematical model for pore development is proposed and shown to correlate satisfactorily, the pore volume and surface area measurements.     

Petrography and anisotropy of carbonized preoxidized coals

Vitrinite-rich samples from a weakly caking and a strongly coking coal have been carbonized both fresh and after preoxidation for 14 days at 105 °C to points within the temperature range 300–800 °C. Conventional reflected-light microscopy shows that pronounced reduction in softening capacity and devolatilization of carbonized preoxidized reactive macerals are accompanied by microscopical features which contrast with those of the same reactive macerais when carbonized fresh. Most noticeable is the retention of the original petrographical structure of the coals when carbonized after preoxidation, even at temperatures of 800 °C. No mosaic is formed in the preoxidized reactive macerals, although a general anisotropy gradually develops; some vitrinitic particles attain a very high degree of anisotropy though all of this development takes place in the solid state. The level and trends of the average bulk bireflectances of both forms of carbonized vitrinite are similar, but the rapid bireflectance rise characteristic of vitrinites carbonized above ≈ 600 °C probably begins earlier in preoxidized than in fresh vitrinites. This could happen if preoxidation raises the aromaticity of the original vitrinite, so allowing reorientation of the lamellae to begin at lower temperatures. Comparisons are made with earlier observations.     

Structure in cokes from coals of different rank

A range of bituminous coals has been carbonized to 1273 K. Polished surfaces of the solid products, carbons or cokes, are examined for optical texture by optical microscopy. Fracture surfaces of the carbons are examined by scanning electron microscopy (SEM). The carbon from the lowest rank coal (NCB Code No. 702) is isotropic and fracture surfaces are featureless. Carbons from coals of ranks 602, 502 are optically isotropic but fracture surfaces are granular (size 0.1–0.2 μm), indicating small growth units of mesophase. In the carbon/coke from a 401 coal, the anisotropic optical texture and grain size are both ≈0.5–10 μm diameter. Coke from a coking coal (301a, 301b) has a layered structure extending in units of at least 20 μm diameter with sub-structures ~ 1.5 μm within the layers, indicating perhaps that the bedding anisotropy of these coals is not totally lost in the fluid phase of carbonization. The carbons from the higher rank coals have the bedding anisotropy of the parent coal. The combined techniques of optical microscopy and SEM (both before and after etching of the fracture surfaces of coke in chromic acid solution) reveal useful detail of structure in carbons/cokes and of the mechanism of carbonization of coking coals.     

Carbonization and liquid-crystal (mesophase) development. 11. The co-carbonization of low-rank coals with modified petroleum pitches

Coals of rank ranging from medium quality coking to non-caking, non-fusible, have been co-carbonized with Ashland petroleum pitches A170, A240 and A200 as well as pitches modified by heat-treatment with aluminium chloride using A170, and by reductive hydrogenation of the A200. The mixing ratio was 7:3, the final HTT was 873 K, heating at 10 K min^?1 with a soak time of 1 h. The optical texture of the resultant cokes is assessed using polished surfaces and a polarized-light microscope using reflected light and a half-wave plate. The changes in optical texture are studied from the point of view of using coals of low rank in the making of metallurgical coke. The optical texture of resultant cokes is modified by co-carbonization and the mechanism involves a solution or solvolysis of the non-fusible coals followed by the formation of nematic liquid crystals and mesophase in the resultant plastic phase. The modified A170 pitch is more effective in modifying optical texture than the A170 because of an increase in molecular weight. The hydrogenated A200 is a very reactive additive probably because of an increased concentration of naphthenic hydrogen. The hydrogenated A200 can modify the optical texture of cokes from the organic inerts of coals and from oxidized, non-fusible coals.     

Effect of prolonged heating on the optical properties of vitrinite

Vitrinites ranging from sub-bituminous to anthracitic rank have been heated at 150 and 350 °C for residence times extending up to 32 weeks. Devolatilization vacuoles develop in all the vitrinites at 350 °C, apart from the anthracitic. Occasional small vacuoles formed in the vitrinites of coking rank at 150 °C are most probably related to gas evolution from liptinites. Slight rounding of the margins of vitrinite particles of coking rank at 350 °C indicates softening, while heating at the longest residence time has been sufficient to allow vitrinites of coking rank to undergo ‘active decomposition’. Mosaic structures have developed at temperatures as much as 125 °C below those normally attributed to the formation of such structures in short-term laboratory carbonization experiments on vitrinites of the same rank. Again, apart from the vitrinites of anthracitic rank, the reflectance of vitrinites shows a rise at 150 and 350 °C that would continue beyond the longest residence time used. At 350 °C a large part of the reflectance increase occurs during the first week of heating. The reflectance data and the derived refractive and absorptive indices indicate that with sufficiently long residence times, changes that are more fundamental than ‘molecular stripping’ must take place, probably involving condensation reactions that introduce increased coplanarity into the vitrinite molecules. The implication of these data to thermal metamorphism of coals and to the normal coalification process is briefly discussed.     

Carbonization and liquid-crystal (mesophase) development. 6. Effect of pre-oxidation of vitrinites upon coking properties

The effects of atmospheric oxidation at 378 K upon the carbonization of a coking and a caking vitrinite have been examined in terms of the origins and extents of development of anisotropic material. The vitrinites, oxidized from 1 to 40 days, were carbonized to temperatures between 618 and 878 K, in open boats under nitrogen at atmospheric pressure, and in sealed gold tubes at maximum pressures of 140 to 310 MPa. Optical microscopy was used to observe, qualitatively, changes in reflectance and in shape and size of the anisotropic material of the carbonized product; morphological changes were monitored by scanning electron microscopy. For both vitrinites, whereas one day of oxidation destroyed coking properties and almost all of the anisotropic development in the open-boat carbonizations, the pressure carbonizations were not significantly affected until after five days of oxidation. Anisotropy still developed by mesophase growth from the plastic phase of carbonization, to produce the shaped, botryoidal material characteristic of pressure carbonizations. Thereafter, although in the pressure carbonizations the particles of coking vitrinite only fused slightly at interfaces to form a coherent product, marked increases occurred in reflectance and in observed anisotropy, showing maxima at nine days of oxidation. Results are interpreted on the assumption that oxidation cross-links the macromolecular structure of the vitrinite substance. The effect of high pressure during carbonization after five days of oxidation is to preserve and perfect the original basic anisotropy of the vitrinites initially stabilized by the cross-linkage of oxygen atoms.     

Coal characterisation by automated coal petrography

Automated imaging techniques were refined to characterise the rank and maceral composition of coals by a full maceral reflectogram of polished coal grain mounts. Precision was improved by processing individual grains in each image separately and correcting within the software for the topography that occurs between the different macerals and minerals in the grains. Maceral group proportions and vitrinite reflectance information extracted from these reflectograms compared well with manual results for a comprehensive suite of Australian coals varying in rank from a mean vitrinite reflectance of 0.48-2.13%. A parameter that combines rank and type calculated from the reflectograms correlated strongly with chemical properties determined by ultimate and proximate analyses. For a limited number of samples, for which coking tests had been performed, this parameter also correlated with estimated coking performance.     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

The pyrolysis of acenaphthylene studied by proton nuclear magnetic resonance

The thermally induced transformations of acenaphthylene during pyrolysis at temperatures up to 800 K have been monitored dynamically by pulsed-proton NMR thermal analysis techniques. Measurements have been made of both the transverse and the spin-lattice relaxation properties of the protons during heating at 2, 4 and 8 K/min and subsequent isothermal treatment for up to 300 min. As well as clearly delineating the melting of acenaphthylene and the formation and decomposition of polyacenaphthylene, these two NMR properties have been used to follow the transformation of the high-temperature pitch to produce anisotropic mesophase and semicoke. It is concluded from these NMR results, together with supplementary information obtained from differential scanning calorimetry (DSC) experiments and from examination of the pyrolysis residues by ESR, NMR and polarized light microscopy, that

• 1.(a) the free radical concentration attained by the intermediate pitch during uniform heating is critical in determining the transformation rate of the pitch, which is found to be greater both for pitches prepared by slower heating and for those treated at higher temperatures
• 2.(b) the preparation of the intermediate pitch by more rapid heating is conducive to mesophase formation during subsequent isothermal treatment because it extends the duration of high molecular mobility, and
• 3.(c) the appreciable concentration of aromatic free radicals in the residue decreases significantly with time after cooling to room temperature if condensation and cross-linking reactions have not progressed sufficiently during the high-temperature treatment of the pitch.

     

Enhancement of plastic properties of inert-rich oxidized cretaceous coals via the water-gas shift reaction

In some cases cretaceous coals from Western Canada contain considerable amounts of inert components. These are of two general types: one resulting from in situ vitrinite oxidation and the other consisting of inherently inert macerals. Such oxidized inert-rich coals may be unsuitable for commercial utilization. In some combustion systems a high proportion of unburnt carbon may remain in the fly ash indicating incomplete combustion of the different macerals. In addition, carbonization and liquefaction are unfavourably affected. The development of a process strategy to permit the utilization of these coals by improvement of plastic properties via the water-gas shift reaction is described. This process is applied to the upgrading of three samples of naturally weathered inert-rich coal from Western Canada demonstrating the transformation from non-coking to coking coal.     

Carbonization and liquid-crystal (mesophase) development. 13. Kinetic considerations of the co-carbonizations of coals with organic additives

Five coals, of rank from an anthracite to a non-caking coal, have been carbonized singly and also cocarbonized with decacyclene, mixing ratio 7:3, in the temperature range 648 K to 823 K, heating at 10 K min^?1, with various soak times. The objective of the study is to derive the basic factors which influence the kinetics of formation of mesophase and anisotropic coke. Accordingly, resultant cokes were polished and surfaces examined by reflected polarized light in an optical microscope. The size, shape and extent of anisotropic development is discussed in terms of the conditions of carbonization and the rank of coal. In these systems a somewhat larger optical texture results in cokes produced at the higher carbonization temperatures. The temperature of onset of growth of anisotropic carbon in co-carbonizations was below that of either the coal or the decacyclene. Reactivities are evidently modified. The origins, growth and coalescence of growth units of anisotropic carbon in these cocarbonizations of coals with decacyclene are demonstrated.     

Speciation and thermal transformation of sulfur forms in high-sulfur coal and its utilization in coal-blending coking process:A review

The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources, and sulfur removal from high-sulfur coal is the most important issue. This paper reviews the speciation, forms and distribution of sulfur in coal, the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis, and the sulfur regulation during coal-blending coking of high organic-sulfur coals. It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization, which raises the need of a combination of current or newly adopted characterization methods. Different from the removal of inorganic sulfur from coal, the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property, particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes. Based on the interactions among the sulfur radicals, sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char, regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is, the high volatile coals with an appropriate releasing temperature range of CH_4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals, and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals. Wherein, the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.     

基氏流动度指标特征分析

通过对炼焦煤基氏流动度指标、黏结性指标、镜质组反射率和挥发分等质量指标的研究,分析了不同煤种基氏流动度指标与其他黏结性指标和质量指标之间的关系,结果显示基氏流动度指标能够很好地反映炼焦煤的黏结特性,基氏流动度指标的最大流动度温度与炼焦煤变质程度呈现良好的相关性,可为炼焦煤质量的全面评价提供参考。     

Chemical structure of coal macerals in Balmer 10 coal and fusinite from Illinois coal as indicated by reductive alkylation

A Canadian Cretaceous coking coal from the Balmer 10 seam, Fernie, British Columbia, was separated by sink-and-float methods into vitrinite and a semifusinite-rich fraction. A portion of the vitrinite fraction was oxidized in air at 100 °C for 72 h to destroy the coking properties. The fresh vitrinite, oxidized vitrinite, and semifusinite of the Balmer coal, and the fusinite from Illinois coal, were each subjected to the reductive alkylation procedure of Sternberg, to cleave the ether linkages and octylate the products. The oxygen functional groups before and after ether cleavage were determined, as were the extractabilities by benzene of the octylated products. Thus the molecular weights of the benzenesoluble fractions of the octylated cleavage products were: fresh vitrinite 1930, oxidized vitrinite 1830, and fusinite 1490. The molecular-weight distribution of the octylated cleavage products was estimated by volatility analysis, which demonstrated the presence of much lower-molecular-weight material. Dilatation analysis of fresh and oxidized vitrinite showed that after cleavage of the ether linkages with potassium in tetrahydrofuran, the two could be brought to the same state. The dilatation behaviour of semifusinite after cleavage of the ether links and octylation showed only contraction, whereas the oxidized vitrinite treated in a similar manner exhibited a large dilatation.     

Study on the structure and gasification characteristics of selected South African bituminous coals in fluidised bed gasification

The gasification characteristics of three South African bituminous coals were investigated in a bubbling fluidised bed reactor. The three coals are similar in rank, but two are inertinite-rich coals and the third has a high vitrinite content. The microstructural characteristics of the parent coals and their resultant chars were determined using XRD, FT-IR, Raman and petrographic analysis. The microstructural changes that occurred in the organic (maceral) and the inorganic (mineral) fractions of the selected coals were evaluated. The change in the carbon structure was correlated to the proportions of inertinite and vitrinite macerals in the coals. High vitrinite content resulted in an increase in the order of the disordered carbon structure after gasification and this leads to greater graphitised ordered carbon structures. While a high inertinite content resulted in low or no structural transformation of the chemical structure. The transformation of inorganic mineral constituents of the coal was correlated to the amount of inertinite present in the selected coals. Higher proportions of inertinite macerals and inertinitic chars resulted in higher proportions of melted minerals. Char samples with low proportions of organic matter resulted in higher proportion of melted minerals covering the char surface.     

新一代透明调理剂——Jaguar Excel

在分子水平上介绍了一种新型阳离子瓜尔胶－Ｊａｇｕａｒ Ｅｘｃｅｌ。它与其它阳离子调理剂相比在头发上有更高的吸附率;无累积副作用,与高分子量二甲基硅油乳液一起使用具有独特,卓越的配伍效果;对受损头发起到修护作用。