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Title: Determination of the effect of different additives in coking blends using a combination of in situ high-temperature {sup 1}H NMR and rheometry

Abstract

High-temperature {sup 1}H NMR and rheometry measurements were carried out on 4:1 wt/wt blends of a medium volatile bituminous coal with two anthracites, two petroleum cokes, charcoal, wood, a low-temperature coke breeze, tyre crumb, and active carbon to determine the effects on fluidity development to identify the parameters responsible for these effects during pyrolysis and to study possible relationships among the parameters derived from these techniques. Positive, negative, and neutral effects were identified on the concentration of fluid material. Small positive effects (ca. 5-6%) were caused by blending the coal with petroleum cokes. Charcoal, wood, and active carbon all exerted negative effects on concentration (18-27% reduction) and mobility (12-25% reduction in T2) of the fluid phase, which have been associated with the inert character and high surface areas of these additives that adsorb the fluid phase of the coal. One of the anthracites and the low-temperature coke breeze caused deleterious effects to a lesser extent on the concentration (7-12%) and mobility (13-17%) of the fluid material, possibly due to the high concentration of metals in these additives (ca. 11% ash). Despite the high fluid character of tyre crumb at the temperature of maximum fluidity of the coal (73%), the mobilitymore » of the fluid phase of the blend was lower than expected. The comparison of {sup 1}H NMR and rheometry results indicated that to account for the variations in minimum complex viscosity for all the blends, both the maximum concentration of fluid phase and the maximum mobility of the fluid material had to be considered. For individual blends, two exponential relationships have been found between the complex viscosity and the concentration of solid phase in both the softening and resolidification stages but the parameters are different for each blend. 30 refs., 8 figs., 5 tabs.« less

Authors:
; ; ; ;  [1]
  1. Nottingham University, Nottingham (United Kingdom). Nottingham Fuel and Energy Centre, School of Chemical, Environmental and Mining Engineering
Publication Date:
OSTI Identifier:
20688439
Resource Type:
Journal Article
Resource Relation:
Journal Name: Energy and Fuels; Journal Volume: 19; Journal Issue: 6; Other Information: colin.snape@nottingham.ac.uk
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; COKING; ADDITIVES; BITUMINOUS COAL; ANTHRACITE; COKE; PETROLEUM PRODUCTS; CHARCOAL; WOOD; COKE BREEZE; TIRES; ACTIVATED CARBON; HYDROGEN 1; NUCLEAR MAGNETIC RESONANCE; CONCENTRATION RATIO; MOBILITY; RHEOLOGY; MIXTURES

Citation Formats

Miguel C. Diaz, Karen M. Steel, Trevor C. Drage, John W. Patrick, and Colin E. Snape. Determination of the effect of different additives in coking blends using a combination of in situ high-temperature {sup 1}H NMR and rheometry. United States: N. p., 2005. Web. doi:10.1021/ef050126n.
Miguel C. Diaz, Karen M. Steel, Trevor C. Drage, John W. Patrick, & Colin E. Snape. Determination of the effect of different additives in coking blends using a combination of in situ high-temperature {sup 1}H NMR and rheometry. United States. doi:10.1021/ef050126n.
Miguel C. Diaz, Karen M. Steel, Trevor C. Drage, John W. Patrick, and Colin E. Snape. 2005. "Determination of the effect of different additives in coking blends using a combination of in situ high-temperature {sup 1}H NMR and rheometry". United States. doi:10.1021/ef050126n.
@article{osti_20688439,
title = {Determination of the effect of different additives in coking blends using a combination of in situ high-temperature {sup 1}H NMR and rheometry},
author = {Miguel C. Diaz and Karen M. Steel and Trevor C. Drage and John W. Patrick and Colin E. Snape},
abstractNote = {High-temperature {sup 1}H NMR and rheometry measurements were carried out on 4:1 wt/wt blends of a medium volatile bituminous coal with two anthracites, two petroleum cokes, charcoal, wood, a low-temperature coke breeze, tyre crumb, and active carbon to determine the effects on fluidity development to identify the parameters responsible for these effects during pyrolysis and to study possible relationships among the parameters derived from these techniques. Positive, negative, and neutral effects were identified on the concentration of fluid material. Small positive effects (ca. 5-6%) were caused by blending the coal with petroleum cokes. Charcoal, wood, and active carbon all exerted negative effects on concentration (18-27% reduction) and mobility (12-25% reduction in T2) of the fluid phase, which have been associated with the inert character and high surface areas of these additives that adsorb the fluid phase of the coal. One of the anthracites and the low-temperature coke breeze caused deleterious effects to a lesser extent on the concentration (7-12%) and mobility (13-17%) of the fluid material, possibly due to the high concentration of metals in these additives (ca. 11% ash). Despite the high fluid character of tyre crumb at the temperature of maximum fluidity of the coal (73%), the mobility of the fluid phase of the blend was lower than expected. The comparison of {sup 1}H NMR and rheometry results indicated that to account for the variations in minimum complex viscosity for all the blends, both the maximum concentration of fluid phase and the maximum mobility of the fluid material had to be considered. For individual blends, two exponential relationships have been found between the complex viscosity and the concentration of solid phase in both the softening and resolidification stages but the parameters are different for each blend. 30 refs., 8 figs., 5 tabs.},
doi = {10.1021/ef050126n},
journal = {Energy and Fuels},
number = 6,
volume = 19,
place = {United States},
year = 2005,
month =
}
  • The effects of blending polyethylene (PE), polystyrene (PS), poly(ethyleneterephthalate) (PET), a flexible polyurethane (FPU), and a car shredded fluff waste (CSF) on fluidity development of a bituminous coal during carbonization have been studied by means of high-torque, small-amplitude controlled-strain rheometry and in situ high-temperature {sup 1}H NMR spectroscopy. The most detrimental effects were caused by PET and PS, which completely destroyed the fluidity of the coal. The CSF had a deleterious effect on coal fluidity similar to that of PET, although the deleterious effect on the viscoelastic properties of the coal were less pronounced than those of PET and PS.more » On the contrary, the addition of 10 wt % PE caused a slight reduction in the concentration of fluid hydrogen and an increase in the minimum complex viscosity, and the addition of 10 wt % FPU reduced the concentration of fluid hydrogen without changing the viscoelastic properties of the coal. Although these results suggest that these two plastics could potentially be used as additives in coking blends without compromising coke porosity, it was found that the semicoke strengths were reduced by adding 2 wt % FPU and 5 wt % PE. Therefore, it is unlikely that more than 2 wt % of a plastic waste could be added to a coal blend without deterioration in coke quality. 35 refs., 11 figs., 3 tabs.« less
  • The high-pressure behavior of zirconium has been examined using the synchrotron X-ray diffraction technique to a pressure of 38 GPa and a temperature of 800 K employing a hydrothermal diamond anvil cell technique. The structural transition from the ω to the β phase was observed. This transition has a negative dP/dT gradient, which is in general agreement with those reported in previous studies. The transition boundary was determined to be, P (GPa)=41.2–0.025×T (K). The negative slope of the transition, dP/dT, determined in our study using the diamond anvil cell technique was less than half that estimated by the previous studymore » using a large press apparatus. - Graphical abstract: Experimental results and phase boundary of the ω–β transition in Zr. - Highlights: • X-ray diffraction patterns of zirconium were measured by the synchrotron experiments. • High-pressure experiments were performed by an external-heated diamond anvil cell. • Phase diagram of zirconium was determined at high pressures and high temperatures. • Phase boundary between omega and beta transition has a negative dP/dT slope.« less
  • When coal is heated in the absence of oxygen it softens at approximately 400 degrees C, becomes viscoelastic, and volatiles are driven off. With further heating, the viscous mass reaches a minimum viscosity in the range of 10{sup 3}-10{sup 5} Pa s and then begins to resolidify. A high-torque, high-temperature, controlled-strain rheometer with parallel plates has been used to study the theology during this process. Under shear, the viscosity of the softening mass decreases with increasing shear rate. During resolidification, the viscosity increases as C-C bond formation and physical interactions gives rise to an aromatic network, but, under shear, themore » network breaks apart and flows. This is viewed as a yielding of the structure. The higher the shear rate, the earlier the yielding occurs, such that if the shear rate is low enough, the structure is able to build. Also, further into resolidification lower shear rates are able to break the structure. It is proposed that resolidification occurs through the formation of aromatic clusters that grow and become crosslinked by non-covalent interactions. As the clusters grow, the amount of liquid surrounding them decreases and it is thought that the non-covalent interactions between clusters and liquid could decrease and the ability of growing clusters to move past each other increases, which would explain the weakening of the structure under shear. This work is part of a program of work aimed at attaining a greater understanding of microstructural changes taking place during carbonization for different coals, in order to understand the mechanisms that give rise to good quality cokes and coke oven problems such as excessive wall pressure.« less
  • To maximize the conversion of low-quality coal into good coke, we investigated the thermoplasticity of various binary blends of caking coals with slightly or noncaking coals using a dynamic viscoelastic technique with a temperature-variable rheometer. Coal blend samples were prepared by mixing two coals (1:1 by weight), which were heated from room temperature to 600 C at a rate of 3-80{sup o}C/min. At the slow rate of 3{sup o}C/min, the blends had a tan {delta} that was generally lower than the calculated value, showing that a negative interaction caused a loss of thermoplasticity. In contrast, at the rapid heating ratemore » of 80{sup o}C/min, the tan {delta} of some blends was higher than the calculated value, indicating a positive interaction that enhanced the thermoplasticity. With rapid heating, the thermoplasticity of each coal itself increased, and their thermoplastic temperature ranges widened with rapid heating. Therefore, rapid heating was effective at converting these coal blends into good cokes. Moreover, even with slow heating, when a combination of coals (Gregory:Enshu, 1:1) showing some thermoplasticity in nearly the same temperature range was blended, a desirable synergistic effect of the blend was obtained. This suggests that blending coal with an overlapping thermoplastic temperature range is important for the synergistic effect, regardless of the heating rate. 15 refs., 9 figs., 2 tabs.« less