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.     

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.     

Carbonization and liquid-crystal (mesophase) development. 20. Co-carbonization of a high-volatile caking coal with several petroleum pitches

A high-volatile caking coal and five petroleum pitches were carbonized singly and coal/pitch systems were co-carbonized to 1273 K in the ratio of 75 wt% coal and 25 wt% pitch. Optical textures of cokes from the single carbonizations and co-carbonizations are assessed in terms of modification to the coalcoke by the pitch and unmodified pitch-coke using a point-counting technique. The pitches differ considerably in their carbonization behaviour. Each pitch can be placed into one of three groups defined in terms of their interaction with the high-volatile caking coal. A passive pitch does not modify the coalcoke but apparently carbonizes independently of the coal. An active pitch modifies some of the coalcoke. No pitch-coke can be detected. A super-active pitch modifies the coal-coke extensively beyond the extent expected from a 25% addition. No pitch-coke can be detected. The effects are related to the ability of the pitch to cause depolymerization of the coal. Quinoline-insoluble material in pitch may inhibit modification.     

Gasification reactivities of optical textures of metallurgical cokes

Optical textures of ten typical cokes before and after gasification in CO₂ were quantified by point counting under a polarized microscope to quantify the reactivities of each type of optical texture. Although absolute values of gasification rate for each texture varied considerably from coke to coke, their relative values were constant regardless of the origin of the cokes. The relative reactivities of flow, mosaic, isotropic and inert textures were 1,1.8,2.8 and 3.0, respectively. The relative reactivity of a single coke calculated from a knowledge of optical textures, was monotonicly correlated with the mean maximum reflectance ($\text{R}\text{?}{}_0$) of the parent coal. This indicates that the high reactivity of coke from a high-rank coal ($\text{r}\text{?}{}_0\text{= 1.8\%}$) is due to factors other than its optical texture. The crystallite height, L_c(002)' of the coke correlated with $\text{R}\text{?}{}_0$ of the parent coal, although the values of L_c(002) varied only from 1.5 to 2.1 nm.     

Effects of weathered coal on coking properties and coke quality

Determinations of weathered coal by petrographic methods, and coking tests in an 18-inch ($\text{≈}\text{1}\text{2}\text{m}$) test oven were used to quantify the effects of weathered coal on coking properties and coke quality. The results show that the presence of weathered coal causes a decrease in coke stability and coking rate and an increase in coke reactivity and coke-breeze generation. Because these effects contribute to increased costs in both the coke plant and the blast furnace, every effort should be made to reduce the amount of weathered coal in coking coal mixes.     

改质沥青配煤炼焦的研究与实践

根据沥青黏结性较好、灰分低的特点,利用40kg试验小焦炉进行沥青配煤炼焦试验,确定配煤方案和配入比例后进行大焦炉试验,最终成功应用于JN60焦炉进行连续生产。沥青配煤的应用,改善了焦炭质量,扩大了配煤的使用范围,降低了焦炭生产成本。     

Effect of low-volatile additives on the structure and strength of cokes

Blends of medium-volatile or high-volatile coals have been carbonized in a 7 kg oven with low-volatile coals (6–16% VM, dmmf). A comparison is made of the strength and structural properties of these cokes with those of the cokes made under corresponding conditions from the medium or high-volatile coals alone. With increasing levels of addition of the low-volatile coals the tensile strength of the blend cokes generally attains a maximum and then decreases. These strength changes are related to changes in porosity, pore-wall thickness and pore dimensions. Coals which display some degree of plasticity and which are weakly caking improve coke quality by altering the pore-structure due to the combined effects of decreasing the pore diameter and slightly increasing the wall thickness. Those additives which are non-caking act primarily as wall thickeners.     

Carbonization and liquid-crystal (mesophase) development. 9. The co-carbonization of vitrains with Ashland A200 petroleum pitch

Vitrains from a wide range of ranks of coals were carbonized singly and also co-carbonized (HTT 1273 K) with 25% of Ashland A200 petroleum pitch. Polished surfaces of the resultant cokes were examined for optical texture in a polarizing-light optical microscope using a half-wave retarder plate to produce interference colours. For the anthracites, there is no modification of either component during co-carbonization. The growth of optical texture from the A200 pitch is not affected. For all caking vitrains the optical texture of coke from the blend system is extensively modified when compared to the optical texture of coke from the vitrain. For the low-rank non-caking vitrains the isotropic coke becomes totally or partially anisotropic in co-carbonization. The mechanism of modification of the optical texture of resultant cokes is related to the formation of nematic liquid crystals, mesophase and the semi-coke. It is not considered that the chemistry of pyrolysis is modified on cocarbonization of the vitrain and pitch.     

Conversion of caking coal into non-caking coal by treatment with sulphur and sulphur dioxide

The effects on the caking properties of coals of reaction between the coals and S₈ and SO₂, have been studied. Caking coals (Akabira, Shinyubari, Zollverein, Indian Ridge, and Big Ben) lose their caking properties when treated with S₈ above 200 °C. For Shinyubari coal the crucible swelling number decreases from $\text{8}\text{1}\text{2}$ to 2 with treatment temperature of 235°C in which 5% of S is incorporated into the coal. The decaking of coal is attributed to thio-ether cross-linkages. Caking coals also lose completely their caking property when reacted with SO₂ at 170 °C. The decaking action of SO₂ is attributed to oxidation of coal in which ether cross-linkages are formed.     

Nuclear magnetic proton relaxation studies of oxidized coals

Coals of NCB rank 301 a (coking), 502 (caking) and 802 (very weakly caking) are oxidized in air at 373 K or 383 K for up to 42 days. Spin-lattice and spin-spin relaxation times, T₁ and T₂ respectively, of oxidized coals are measured using a Bruker SXP 4–100 and FT spectrometer. Free radical concentrations in the coals are obtained using a JES PE e.s.r. spectrometer. Infrared spectra of oxidized coals are obtained and optical textures of cokes from fresh and oxidized coals are assessed by optical microscopy. For two coking coals, decreasing values of T₁, and increasing concentration of free radicals occurred with oxidation at 383 K to 16 and 28 days. Thereupon values of T₁, increased and free radical concentrations decreased with further progressive oxidation. At the point of inflexion in properties, resultant cokes from the coals ceased to shown any anisotropy in their optical textures and became isotropic resembling cokes from low-rank coals. For the caking coals, T₁ increased at all stages of oxidation to 42 days with decreasing concentrations of free radicals. Two values of T₂ were found in each coal corresponding to a rigid and mobile component ((T₂)_r < (T₂)_m). The rigid component (T₂)_r was not affected by oxidation but values of (T₂)_m decreased with increasing duration of oxidation. It is considered that coking and caking coals exhibit different effects of oxidation with perhaps phenols and quinones in caking coals acting as inhibitors to the growth of stable free radicals. Oxidized coking coal may behave like fresh caking 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.     

焦炭强度指标间的关系研究

通过１０种单种煤炼制的７ｋｇ焦炉焦，７个钢铁公司的入炉焦和风口焦，测定他们的米库姆转鼓强度、Ｉ－转鼓强度、显微强度、结构强度、抗拉强度和焦炭光学组织，从中揭示他们之间的内在关系。     

Carbonization and liquid-crystal (mesophase) development. 22. Micro-strength and optical textures of cokes from coal-pitch co-carbonizations

This study examines the micro-strength and optical textures of a laboratory coke from a base-blend of Freyming and Pocahontas coal (wt ratio, 1:1) and of cokes from the co-carbonization of the blend, with each of five petroleum pitches in various proportions. Coke pieces, 212–600 μm, from the micro-strength test are assessed in terms of origin and propagation of cracks induced by the test. Always, the addition of pitch to the base-blend improves the strength of the resultant cokes, the pitches behaving differently. A qualitative, subjective appraisal of results indicates that increases in coke strength are associated with relative abilities of pitches to interact with the coals to produce a fluid phase, of solution of coal in pitch, which gives an ‘intermediate’ coke with an optical texture of mozaics. This intermediate coke strengthens the bonding at interfaces. Cracks originate predominantly from the shrinkage cracks in the domains of Pocahontas coke. Mozaic structures tend to resist crack propagation. The coal/pitch system may flow around coal particles so containing incipient crack formation in resultant coke particles.     

High-temperature 1H n.m.r. study of oxidized coal

Two coking coals, a caking and a non-caking coal are examined in a Bruker pulsed ¹H n.m.r. spectrometer in the temperature range 293–730 K. One coking and the caking coal are oxidized in air at 383 K for 13 days. Temperatures of signal appearance and loss are noted as well as the temperatures of minimum signal half-peak width ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$). There occurs no change in the above three temperatures with oxidation of the coals. The variation of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) with temperature of the coal is also measured. Changes in ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) are more pronounced for the caking coal. The softening and solidification temperatures are below and above, respectively, those reported using the Gieseler method. Values of ($\text{ΔH}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$) increase beyond the minimum value as the fluidity continues to increase. This may be caused by an increase in average molecular weight of constituent molecules and/or an increasing concentration of free radicals in the fluid phase. This experimental approach may afford a new method to characterize coals which are to be used in liquefaction processes.     

Growth and coalescence of mesophase in pitches with carbon black additives and in coal

The techniques of polatized light optical microscopy and of washing the surfaces of solid pyrolysis products with chloroform prior to SEM examination are used to monitor the growth and coalescence of growth units of mesophase in a petroleum pitch, a coal extract and a caking coal. Additions of 1 wt% of carbon black retard growth and coalescence and promote clustering of these units because of adhesion of carbon black particles. This has the effect ultimately of reducing the size of the optical texture in coke from the coal extract, but not with coke from the petroleum pitch which has lower viscosity. With the coal, mesophase growth units tend to form clusters and do not coalesce. Mesophase can form an anisotropic skin on the inside of developing pores (bubbles) in the fluid phase and this may limit their growth.     

Thermogravimetric investigations in prediction of coking behaviour and coke properties derived from inertinite rich coals

The coal quality, temperature, pressure, heating rate, various processes and reactor type affect coking behaviour of coal and resulting coke properties. Several petrographic and chemical methods were proposed earlier for prediction of coking behaviour of coals. Inertinite rich coal samples (I^mmf>30 vol%) having different petrographic compositions were selected for thermogravimetric investigations (DTA, DTG and TGA) and their coking behaviour was studied. The petrographic build up, micro-structural properties (porosity and cell wall thickness) and mechanical strength of the resulted cokes were also investigated. ΔH and ΔH_max (the main endothermic area of heat absorption and fast absorbing main endothermic area, respectively) were distinguished in DTA curves. ΔA and ΔA_max (the main decomposition area and fast disintegrating main decomposition area) under DTG curves were identified. ΔH_max/ΔA_max shows good correlation with Roga's indices (RI, caking properties) as well as with petrographic caking ratio (PCR). The coarse mosaic content of cokes seem to depend on LΔT_max/ΔT_max (ratio of weight loss during fast decomposing main reaction to temperature difference) under DTG. L^mΔT/ΔT (ratio of weight loss during main decomposing reaction to temperature difference) under DTG exhibits correlation with p₁ (mean pore size) and t₁ (mean cell wall thickness) of cokes. ΔA_max/(L^mΔT_max) also indicates good relationship with mechanical strength of cokes. (L^mΔT_A−T_B)/(L^mΔT) (i.e. ratio of weight loss during main endothermic reaction under DTA to weight loss during main decomposing reaction) appears to have relationship with DD (compactness) of cokes. The course of main endothermic reaction/main decomposition reaction under DTA, DTG and TGA seems to govern coking behaviour and the resulting coke strength, which in turn is controlled by microlithotypes.     

Oil-cum-gas-fired experimental coke oven developed at CFRI and the correlation studies of its coke with commercial oven coke

Assessment of the coking behaviour of coals and blends by conducting coking tests in experimental coke ovens still continues to be the most reliable method and is extensively used all over the world. The oil-cum-gas fired experimental coke oven developed at CFRI has a coal charging capacity of 1100 kg and simulates industrial carbonising conditions. The oven is capable of intermittent operation and can be brought up to working temperature within 36 hours.Correlation studies of coke quality were carried out by conducting a series of coking tests on the same blend, carbonised under similar conditions in the CFRI experimental coke oven and the commercial coke ovens of Bokaro Steel Plant. The study has revealed that the physical strength of the CFRI oven coke compares favourably with the Bokaro oven coke. M₄₀ and M₁₀ indices of the commercial oven coke can be predicted fairly accurately from the results of CFRI oven coke.T-tests performed on the shatter results showed that at 5% probability level there was no significant variation between the shatter indices of both cokes. The quality of the gas produced from the CFRI test oven was very similar to that of the gas produced from the Bokaro ovens.     

Disclinations in the optical texture of a high-rank vitrinite coke and a petroleum needle-coke

The microstructure of coke formed on carbonization of a low-volatile bituminous rank vitrinite (NCB Classification 204), at a heating rate of 60 °C min^?1, was found to consist largely of coarse-grained mozaic and domain type optical texture. The domain optical texture possessed a variety of optical structures, e.g. $\text{‘X’}$ and $\text{‘Y’-}\text{type}$ crosses and nodes, characteristic of it having passed through a nematic liquid crystal stage (mesophase) during carbonization. These structures are compared with, and found equivalent to, disclination structures found in the domains of a petroleum needle-coke, the surface of which had been gasified to reveal the underlying graphitic structure. The formation of disclination structures in the domains of the coal-coke is strong evidence for the formation and coalescence of mesophase during its carbonization as a result of the very high heating rate used.     

A mechanistic study of hydrogenation of coal. 2.

In Part 1 the authors reported that liquefaction of coal by hydrogenation in the presence or absence of vehicle and with or without catalyst progresses with characteristic variations of the reaction order. In the present paper, the roles of temperature, hydrogen, vehicle and catalyst have been studied using a free-radical scavenger such as p-benzoquinone or iodine. Based on these results, a set of characteristic reactions has been identified from which the following overall rate equation has been derived: $\text{d[P}{}_{\mathrm{m}}\text{]}\text{dt}\text{= β}{}_1\text{[C] + β}{}_2\text{[C]}{}^2\text{+ β}{}_3$ where [P_m] denotes gas, and benzene-soluble products, [C] represents the percentages of organic matter in coal and benzene insoluble intermediates, and β₁, β₂ and β₃ are constants. The rate equation thus explains the experimentally observed variation of the reaction order, which depends on the predominance of a particular group of reactions. It has been postulated that pyrolysis is the main driving force, and that hydrogenation of coal either with gaseous hydrogen or by hydrogen-donating vehicle is basically influenced by reactions involving free radicals.     

Dependence of viscoelastic properties of a carbon paste on grain size of coke

Measurements of viscoelastic properties of carbon paste with various coke size distributions were carried out by using a simple compressive creep apparatus. It was found that the carbon pastes with the finer grain size of coke show larger values of steady-state viscosity $\text{}\text{?}$gh and smaller values of steady-state compliance J_e. The experimental data of $\text{}\text{?}$gh and J_e were numerically fitted by taking into account the weight averaged volumes of coke grains. The shift factors used in the time-temperature superposition of creep compliance functions are not dependent on the grain size distribution, and their temperature dependences are essentially the same as that for the pitch itself.