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Kinetic

2. Rapid entrained

studies
pyrolysis reactor

of rapid oil shale pyrolysis:
of oil shales in a laminar-flow

Ming-Shing Shen, Alain and Gary J. Morris?

‘*, Lawrence P. LUI

J. Shadle,

Guo-Qing

Zhangt

Morgantown Energy Technology Center, Morgantown, tDepartment of Mechanical Engineering, West Virginia 26506, USA (Received 26 March 1991; revised 31 May 1991)

WV 26507, USA University, Morgantown,

WV

Rapid pyrolysis of Kentucky New Albany shale was conducted in a laminar-flow entrained reactor (LFER) to obtain a fundamental understanding of thermal reactions, which occur during high-heating-rate retorting processes. The reactor configuration was designed to simplify operation and allow accurate modelhng. Temperature characterization and flow visualization in the LFER were conducted to provide the data necessary to proceed with a kinetic study on the rapid pyrolysis of oil shale. The reactor with gas preheaters was constructed to achieve high particle heating rates and to feed oil shale fine particles generated from beneficiation. The rapid pyrolysis of raw and beneficiated oil shales was carried out in nitrogen at temperatures between 700°C and 85O’C, with gas preheat temperatures up to 98O’C. For each temperature, the sampling probe was set at different positions along the length of the reactor tube to obtain different residence times. A pyrolysis kinetic model of LFER has been developed to calculate the particle heat-up rate and residence time under each set of conditions. Comparisons are presented to evaluate the effects of beneficiation, temperature and heating rate as well as residence time. The effects of particle size and gas environment on heat transfer rates and conversion yields were also studied, and the results were used to validate the heat transfer model and to evaluate the imnact ofdevolatilization behaviour on shale combustion in a circulating fluidized-bed reactor.
(Keywords: oil shale; pyrolysis; kinetic)

Oil shale research at the Morgantown Energy Technology Center has been in high-heating-rate oil shale pyrolysis using flash lamp and entrained flow reactors to simulate the rapid heat-up attained in fluidized-bed combustion and retorting processes. Flash lamp pyrolysis studiesle3 on small micrometre-sized shale particles provided mechanistic insight into the nature of thermal reactions that occur during rapid retorting processes. The overall conversion of shale kerogen to liquids plus gases is higher for flash pyrolysis conditions than for slow-heating processes such as in Fischer Assay and thermogravimetry research’. The rate of the initial phase of kerogen decomposition in flash pyrolysis is extremely rapid. Complete conversion of the kerogen in oil shale can be achieved in a millisecond time frame; however, a large portion of the product is gas. Compared to slow-heating processes, flash lamp pyrolysis products: (1) contain more unsaturated gas species (benzene, toluene and xylenes) and heteroatomic liquid species; (2) are higher in heavy molecular weight liquids; and (3) have greater gas to liquid ratios’. We found that the controlling reaction pathways that govern liquid quality are determined by the heating rate (incident flux), while the overall conversion and the extent of cracking, polymerization or condensation reactions
Presented at ‘Eastern Oil Shale Symposium’, 6-S November 1990. Lexington, KY, USA * Present address: EC&G Washington Analytical Services Center, Inc.. Morgantown Operations, Morgantown Energy Technology Center, 3610 Collins Ferry Road, Morgantown, WV 26507, USA

are determined by the peak temperature (net flu~)~. We found that the liquids from retorting at elevated temperatures were mainly high molecular weight aliphatic components. The process conditions that affect the nature of these products are also expected to affect the nature of the yields and product distribution. We found that shale pyrolysis mechanisms are heating rate dependent: the number of kerogen decomposition pathways are more diverse at high-heating rates than at low-heating rates. The optimum conditions for producing liquids from rapid retorting of oil shale is at a slower heating rate than could be attained in a flash lamp, thus, leading to the development of an entrained reactor. Many studies on the rapid devolatilization of coal have been conducted using entrained reactors4P9; however, the resulting kinetic rates from these and other types of rapid heating experimentsloP13 vary by several orders of magnitude. Several researchers4.5.7.9.12 report that the kinetic rates for coals of different rank were within a factor of 2 to 5 when determined in the same reactor, while the rates obtained for the same coal rank, but from different research groups, varied by several orders of magnitude. Thus, coal type is not the reason for the variations reported. The inconsistency in these rapid heating experiments has been cited as caused by variations in estimations of particle temperature history’-“. Temperature-dependent variations in the thermal properties and the physical structure of coal are often cited as one potential cause for the uncertainty in the temperature histories of coal in rapid heating

0016-2361/91/11127748 c 1991 Butterworth-Heinemann

Ltd.

FUEL, 1991, Vol 70, November

1277

00 35. 1991. We present a critical assessment of the factors involved in determining shale pyrolysis rates using the LFER.32 5. An auxiliary gas vent outlet was installed at the top of the solids reservoir chamber to vent the nitrogen gas required for fluidization in excess of that needed for primary gas injection to the entrained reactor. Proximate and ultimate analyses are presented in Table 1. The raw shales were crushed once through a hammer mill.69 1. The result was a feeder that provided a continuous flow of well-dispersed particles rather than clusters of particles. A collection probe was used that traversed the reaction zone to quickly quench the entire product stream. there is some evidence that this happens.26 0.16 1. which flows.00 17. often referred to as metaplast. The particle densities were measured using mercury porosimetry.09 0. EXPERIMENTAL Samples Experiments were conducted with Colorado shale.79 0.61 56. a porous gas distributor was inserted in the bottom of the solids container and an auxiliary gas line was introduced below the distributor to permit fluidization of the solids. During operation. The geometry of the reactor system was simplified in design to minimize the effect of mixing zones on residence time.43 1.‘) Mean particle diameter (pm) 21. One of the reasons that most experimentation in entrained reactors is conducted with particle sizes >40 pm is that static forces that result in cluster formation tend to be much lower in larger particles5v798. final temperature.00 13.69 1. Enough similarities exist to other analyses for the evaluations made here to be applicable to other rapid devolatilization experiments. New Albany shale and beneficiated New Albany shale in the LFER. The injection probe outlet was located at #the inlet of a Lindberg three-zone tube furnace that was maintained at reaction temperature. Vol 70. a 5 cm inside diameter.60 70. While the physical structure and thus the physical properties of coal particles are dominated by the formation of a melt. swells and becomes glassy at various stages during heatingi4. much more reliable. particularly heating rate. While this configuration permits complete collection of all particles. The beneficiated New Albany shale was prepared by the Mineral Resources Institute. This important distinction makes the estimation of thermal and physical properties. Thus.97 64.79 4.58 0. The syringe pump feeder was modified to accommodate oil shale fine particles generated from beneficiation.5 pm ceramic thimble filter used to collect the solid residue. and to facilitate modelling the Bow.89 135. sieved and then aerodynamically cleaned and separated with the turbo classifier at the Fluidization Research Center of West Virginia University.79 59.00 79. providing a well-defined residence time within the reactor4. particle size. The kerogen in oil shale is such a complicated heterogeneous mixture of organic compounds that the reported pyrolysis kinetics are undoubtedly an average for many different reactions that give the oil product. Immediately downstream from the collection probe was a 0. Both the injection probe and collection probe were water-cooled.02 5. density and diameter.66 149. shale type and grade. heat capacity.03 27. and introduced to the reaction zone using an injection probe.Kinetic studies of rapid pyrolysis: Table 1 Composition of samples Amount Colorado Composition (dry) Organic matter Mineral matter. The primary objective is to determine the kinetics for shale devolatilization at short residence times and high-heating rates. the physical structure in oil shale is dominated by the mineral matter. the observed weight loss is only the light oil that is not condensed and the heavy oil that deposits on the walls of the 1278 FUEL. it has the disadvantage that condensible liquids may deposit back on the spent shale. Fast heat-up and subsequent rapid quench in this system enable the study of the initial stages of retorting.20 4.76 0.14 0. Alabama. LTA C or8 M-S. This aided the breakdown of particle clumps and allowed even fluidization. To study the causes and effects of oil yield enhancement caused by rapid heating. the solids feed bed was slumped several times prior to fluidization by pressurizing the solids reservoir and releasing the pressure using a valve in the vent line. at least when the shale particles contain a normally representative distribution of minerals and kerogen. using fine grinding followed by froth flotation. and the pressure required to fill the interstitial particle volume was determined using non-compressive. shows a schematic diagram of the reactor set-up. entrained in a nitrogen carrier gas (primary gas). November . the gas contacted the entrained oil shale at the probe exit to heat the shale and primary gas to the desired temperature. and since extrapolation for rapid heating rate applications can be risky. Shen et al. Rapid heating of oil shale involves complex mass and heat transfer effects and chemical reactions that are dependent on a wide range of parameters.18 2.82 86.11 . Entrainedflow Figure 1 reactor (wt%) New Albany Beneficiated Li” H N S (total) Ash Moisture (X as recovered) Particle density (g cm-3) Fischer Assay (I t . Measuring kinetic parameters at rapid heating conditions is necessary since there is some variability in the low-heating rate data. Preheated gas (secondary gas) was introduced to the reactor zone through a flow straightener. non-porous glass particles ground to similar sizes according to the technique recommended by Gan and co-workers’ 5.98 0.04 52.37 1. The elemental analyses suggested that the beneficiation resulted in a three-fold enrichment over the raw shale.18 11. laminar-flow entrained reactor (LFER) was constructed to achieve heating rates approaching those anticipated in a fluidized bed.21 1. The position of the cooled collection probe was adjusted to control residence times’.14 3. It is likely that researchers who failed to observe the expected particle size dependence4 caused by differences in heat transfer rates were feeding large clusters rather than discrete particles. such as thermal conductivity. In fact. To disrupt these clusters.01 79. Oil shale particles were fed from a syringe pump feeder.20 experiments 8-9.50 79.

1991. The sum of the primary gas and the shale represented a thermal load of < 10% of that FUEL. volatiles that evolve from the minerals during pyrolysis. the organic conversion rate was determined by using an ash tracer techique. The results were modified from a daf basis to a dmmf basis by correcting for the mineral matter as determined from the low-temperature ash (LTA). and so ample heat was available to ensure that there were no heat limitations or requirements to make up significant portions of the heat in the reaction zone. because it could be washed out in a Soxhlet apparatus in 2 h. separate tests at different residence times were conducted by setting the sampling probe at different positions along the length of the reactor tube. toluene. The gas profiles were characterized using the techniques of Flaxman and Hallett and the operation was established to be steady laminar as described elsewhere16. For each set of conditions. November 1279 .O from hydrated minerals. SOLIDS CARRIER GAS 4 ‘A 20 PSI HEATING GAS “-4” ““I I I t -_. 1077 and 1125 K in a nitrogen atmosphere.4 and 13. available in the secondary gas stream. In an entrained reactor. such as CO.-S. from the decomposition of carbonates or H. The furnace temperature was set to be isothermal using a cluster thermocouple prior to each test run as presented previously16.= proximate ash in dry oil shale and A = proximate ash in dry spent shale. The amount of solid spent shale was collected and weighed and its ash content was determined. Vol 70. Vibrator Second Preheater ST Adjusting Figure 1 Schematic diagram of laminar-flow entrained reactor water-cooled collection probe. while bitumen would continue to be extracted from shale after 24 h.0 1 min-’ pressure. Nitrogen was used as the primary and secondary gas at standard temperature and with 0. However. The oil shale particles were pyrolysed at 976. Shen et al. Flow visualization tests ensured that proper inlet design and operating conditions were sufficient to prevent dispersion of shale particles and to ensure uniform treatment conditions for all particles. Shale was fed into the reactor at a rate of -4 g h. the temperatures of the furnace walls and the entraining gas were independently controlled to match reactor gas and wall temperatures. - First Preheater L In - . In the LFER.Kinetic studies of rapid pyrolysis. The amount of oil that condensed on the spent shale and the filter was determined by simply washing with an organic solvent. Shale particle temperature and shale flow rate must be determined to measure the kinetics of oil shale pyrolysis. The extract was distinguished from what we typically consider as bitumen. The equation for the ash tracer method for calculating weight loss is (1) where AW=weight loss per cent (daf basis). 1026. respectively. will report as weight loss in this type of analysis. M. For each temperature.‘. A. the environment temperature and the entraining gas flow are critical parameters in determining the shale particle temperature and residence times.

were determined as functions of particle temperature.=CD. The primary jet was introduced at a higher linear velocity than the secondary stream so that initial particle velocity was higher than gas velocity. It is accepted that some reaction could have taken place in the collection probe during the particle quench but this was considered a relatively small error. Since there was a dilute flow. =shape factor between the particle and wall and pK = organic density (g cmm3). 976. 1077.d. Because instantaneous equilibration of the primary and secondary gas velocities was assumed. are shown in Figure 2 for Colorado shale.This was because the New Albany shale had a slightly larger particle size and higher density. based on similar heat transfer mechanisms.’ K ’ s._. and gas and shale heat capacity.5 I 0.. cp = particle emissivity (0. 1125 1280 FUEL.2 I 0. Convective and radiative heat transfer relationships and the heat of reaction for the control volume were used to calculate the particle temperature during the period immediately following injection into the LFER: Typical particle velocity profiles in the reaction zone. Particle heat-up was modelled as the sum of the convection plus radiative heat input minus the heat of reaction. The particle velocity reached a stady-state value at -0. No attempt was made to model the cooling rate of the sample. Particle acceleration was modelled as the sum of the drag force and gravity: d2Z d. November . Fluid” and particle properties’8-21. RESULTS AND DISCUSSION Particle trajectory ( particle volume < gas volume 1 10000 > The particle was approximated as a homogeneous.1 0. solid-solid interactions or solid-wall interactions. Tp.Kinetic studies of rapid pyrolysis: M. the particles were fully entrained and flowing at near the velocity of the gas at -90 cm s-l.(VgP I’. 1026. as a function of time. C.3 s when the gas flow reached a fully developed state. d. capacity (J cm -3 K-l). = drag coefficient and G =acceleration of gravity.4%.’ ). The assumption of instantaneous velocity equilibration must be investigated further.03 s. The ash recovery efficiency for all of these experiments was >98%. viscosity. For beneficated New Albany shale. b. since flow visualization tests indicated that the central jet was kept intact and thus may have penetrated into the flow profile of the secondary gas. while the terminal velocity was much less at only 10-20 cm s-l. The distance that particles travel. = convection heat transfer coefficient (J cm. drag forces decelerated the particle until it approached the gas velocity. Shen et a I. The average standard deviation from four sets of duplicate measurements of the weight loss was k 1. F.9 for oil shale). 1991. 50 _I I 0. Equation (4) was solved numerically for distance Z as a function of time. Vol 70. as a first approximation. which corresponds to a precision of k 3. = particle heat VP =particle volume (cm3). the conversion rate of oil shale pyrolysis was assumed to follow the Arrhenius first-order rate expression discussed previously16. t. New Albany shale equilibrated at slightly higher velocity than Colorado shale. where pp = particle density (g cm . The arithmetic mean of particle temperature and the bulk gas temperature were taken as the temperatures of the fluid boundary layer: T=Tp+Tp f -I (2) L Thermal mixing of the primary and secondary gas streams was assumed to be instantaneous. The geometry of the reactor system was made simple to minimize the effect of mixing zones on the residence time and also to facilitate the modelling of the flow velocity and temperature profiles. d. The reproducibility of these measurements was tested by comparing the results of replicate tests at the same conditions. thermal conductivity. which was expected to be approximately the same as the heating rate. spherical particle.4 (set) I 0. it was reasonable to consider a single particle as the control volume: where C.0 I 0. Temperature velocity profile in the reaction zone for (K): a. including gas density. After this point.6 0 17 Figure 2 Predicted particle Colorado shale.9% at the 95% confidence limit. = particle diameter (cm). -S. Particle trajectory Equation (3) was solved numerically to find the particle temperature. The gas must first cool by contacting the cold walls but the smaller diameter in the collection probe (relative to that of the reactor) provides better gas contact and relatively high gas convection rates. calculated from Equation (4).3).)‘+G (4) model The reactor was designed to provide short reaction times without the complications caused by mixing. c. was also a function of time. A minimum velocity is predicted at -0. The particles then accelerated with the gas along the reactor centreline as the laminar velocity profile developed. 2. The profiles for New Albany shale and beneficiated New Albany shale were similar. h.3 Time I 0.

Kinetic studies of rapid pyrolysis: M.7 0. The fit between experimental data and 5 2 E 's 8 . +. This suggests that vaporization of the products may be controlling the initial devolatilization rate.3 0.7%. 1125 the initial particle velocity was higher but equilibrated at lower velocity because of its fine particle size and lower density. 1125 data and curves calculated shale. this type of analysis was deemed appropriate for comparative purposes. 1077. the weight loss was normalized to the maximum yield.0 0 5 10 15 20 25 30 35 40 45 50 -1 55 Distance (cm) Figure 4 Comparison of experimental data and curves calculated using the kinetic parameters for New Albany shale.4 0. The small 0. beneficiated shale particles. The experimental data compared with the model curve fits are shown in Figure 4. Temperature (K): A. The initial increase in particle temperature of the Colorado shale was greater than that of New Albany shale.6 0. Typical temperature history profiles for shale particles at the radial centre of the reaction zone are displayed in Figure 3. n . Preliminary data on toluene extraction of the spent shale residues indicated that heavy oils condensed on the solid particles either in the gas stream or in the collection thimble. This was also because the New Albany shale had a slightly larger particle size and higher density.2 0. 1026: +. FUEL. In a single first-order reaction model. the asymptotic yield was 13. 1077. The temperature dependence was greater for beneficiated shales. The presence of clays that are known cracking catalysts would favour the formation of gas over liquids. At the present time.7%. The rate data for the New Albany shale exhibited a general consistency with literature rate data.g Ii : s E . The extraction yields were greater in the Colorado shale than in the New Albany shale.2% for the New Albany shale. c.7 0.3 I 0. 976. the initial temperature rise was very fast indeed.0 I 0. the temperature dependence appeared too low and systematic variations existed in the fits. b. 1026. The experimental data agreed with the model fits within the experimental confidence limits. being more in line with extrapolations from the literature at lower reaction temperatures.5 0.6 0.1 ms because of the small particle sizez2. In Figures 4 and 5.4 I 0.6 I 0. 976. The beneficiated shale particles reached the final temperature in .9%. d. Temperature (K): a. In any case. the maximum yield was assumed to be the asymptotic yield. The maximum volatile yields corresponded to -70% of the organic matter (Figure 5). For the fine. In the absence of other effects.2 I 0. Such a vaporization process would be more important in the richer particles of the beneficiated shales because of the larger heat requirements and mass fluxes. Temperature (K): A. Although this is not completely consistent with existing evidence on oil shales. this corresponded to a volatile yield of nearly 95% of the organic matter in a period of < 1 s. 1026. was much higher than that for the raw New Albany shale. especially at the lower temperatures22.1 -1 0 5 lb 15 20 25 Distance 30 (cm) 35 40 45 50 55 Figure 5 Comparison of experimental using the kinetic parameters for Colorado 976: n . 1077.5 I 0. reducing the contribution of its terminal velocity”.-S. Vol 70. w* at the highest test temperature. 23. llOOG e 5 5 & r-" f m 4 r L? 500400300 I 0.g 3 0. however. 1991. 1125 - 3 2 k . The conversion rate of Colorado shale was also normalized to its asymptotic yield at 14. Shen et al. When the weight loss data is analysed based on total mass of organic material lost. the beneficiated and the raw New Albany shales exhibited comparable devolatilization rates ~ at least at the lowest temperatures. the maximum yield is independent of temperature. the distribution of ~olatiles into gases and liquids is not known quantitatlvely. having a relative standard error of 3. 0.1 0.6 0.5 1 When analysing the weight loss data in terms of a decomposition reaction with first-order dependence on the concentration of shale organic matter. The maximum yield for the beneficiated New Albany shale**. November 1281 . 0. particle size and heating rate.7 lOOO900aoo700600- Time (set) Figure 3 Predicted particle temperature profile in the reaction zone for New Albany shale. 0. Analysis of pyrolysis rate data beneficiated shale particles heated quickly to reach the final temperature.1 I 0. but the depletion of reactive starting material was notably slower than that for the raw shale.6 0.

For instance. The temperature dependence of the Colorado shale was intermediate between that of the raw and beneficiated New Albany shales. Shen et a I. This minimizes the possibility that individual particles of kerogen or minerals will skew the data. On the other hand. the conversion increased from 14. One implication from this work is that the heat transfer calculations in all studies that assume spherical particles will grossly overestimate the volume of irregularly shaped. The trend 1282 FUEL.Kinetic studies of rapid pyrolysis: M. In fact. Differences arise between experimental data and model calculations for the small particles only. and so it has about a 40% higher area to volume ratio. Scanning electron microscopy (SEM) photomicrographs of the shales and subsequent image analysis indicated that the sphericity (ratio of the sphericalequivalent diameter to the spherical diameter) was 0. At this size fraction. This would suggest that a set of parallel reaction pathways may not be necessary to explain rapid pyrolysis rate data for the western oil shales. and. but there might be a cluster formation. causing some segregation of kerogen and mineral components.2 to 18. the thickness of these particles could have been significantly smaller than assumed. These could be a result of several things. the fact that the eastern shale responded favourably to the rapid heating experiments indicated that the pyrolysis mechanism in an aromatic shale follows a set of parallel reaction pathways such that aromatics not immediately evolved undergo retrogressive reactions to form char. there was little segregation of components and the particles retained a representative mixture of kerogen and minerals. Obviously. a dimensionless parameter. an intraparticle temperature gradient is insignificant. The spherical-volume equivalent size of the shale particles are reported in Table I as determined using the Coulter counter technique and assuming an ellipsoid geometry. while the higher heat conductivity will produce a higher heating rate.5 ms.2% at 850°C. the calculations result in higher thermal inertia and thus lower heat-up rates. This ordering is consistent with the suggestion that the early stages of rapid shale devolatilization are controlled by the rate of vaporization where there is a dependence on oil shale grade. Vol 70.125 pm. Smaller particles had longer residence times because of slower particle velocities. These calculations indicate that for small non-reacting shale particles. If the net heat flux is comparable to the rate of devolatilization. which would. and thence deposit as a coating on the external surfaces of particles. these particle sizes may be smaller than the thickness of the bedding layer. lower viscosity and higher heat conductivity than nitrogen.6 1 t. the kerogen conversion. recent evidence obtained using temperature and particle size measurements on single particles suspended in an electrodynamic balance is inconsistent with this explanation’ ‘. November . On this basis. if a Colorado oil shale (135. the error in assuming that the particle temperature is uniform is < 5% when the particle size is < . probably because of the lower coking tendency of these highly aliphatic kerogens. the rates of heat transfer to the particles are much higher than the rates of heat transfer within the particle. Additional heat tramfer considerations Experiments on Colorado oil shale with helium gas were also conducted to evaluate mass and heat transfer effects. Furthermore.7%. First of all. while that for external shale heating is -80 ms. Experiments on Colorado oil shale with different particle sizes were conducted to evaluate mass and heat transfer effects. -S. In addition.7 to 18. the conversion (weight loss fraction based on shale) increased from 12. to determine the relative resistance for heat transfer externally (to a particle) and internally (within a particle). 1991.0 to 17.96-0. Helium has a smaller density. however. non-spherical particles. The smaller density and viscosity will generate a shorter residence time. affect the heat and mass transfer rates. This situation has been observed when repeated fine grinding to a small particle size (< 100 pm) was desired. The higher heating rate and shorter residence time would enhance the pyrolysis conversion rate. a cube having a characteristic length (largest dimension) equal to that of a sphere has a nearly equal surface area but only two-thirds the volume. the model assumes a single particle as a control volume. Particle size considerations The optimum particle size for these raw shales was found to be 170 by 200 mesh 23. the once-through grinding technique minimizes the potential that kerogen will become fluid because of heat and compression during grinding. Model calculations indicated that particle size was a most important parameter in determining particle temperature history in the LFER. the conversion efficiencies in the western shale were not significantly higher than those obtained at slow-heating rates. This has been assumed to be because the heat transfer coefficient was underestimated. respectively.97. The results indicated that using helium as the carrier gas resulted in an increased weight loss of 6% at 800°C and an increase of 14. Since the spherical particle assumption minimizes the surface area to volume ratio. At 85O”C. the kerogen conversion in such externally coated particles would experience unnaturally large heat and mass transfer rates. thence.‘) is heated in a hot nitrogen environment (lOOO’C). decomposition takes place during heat-up. Recent attempts to measure coal particle temperatures in this type of reactor have indicated that the heat-up times are faster than models estimate’. In addition. This magnitude is not inconsistent with the effects expected because of external heat transport to the particle. calculated curves was not quite as good as for the New Albany shale. the SEM is a two-dimensional technique and the third dimension was assumed to be the same as the smallest measured length.1 to 19. however. in turn. possibly because of the complications from mineral carbonate decomposition and heavy oil material condensation. For example. The model also assumes the primary gas heated up instantaneously and does not take into account the heat transfer of primary gas around the particle. The results indicate that as the mean particle diameter reduced from 70 to 63 to 60 pm. A characteristic heating time’ for the intraparticle heating of shale particles of 70 pm is . Smaller particles heat up more quickly than bigger particles at the same residence time. especially for the raw shale in which the particle size was equal to or larger than the thickness of the bedding layer23. Transient heat transfer equations have been solved24 using the Biot number.7% at a reactor temperature of 800°C.

For a given temperature. Shen. There were also many C=O and C-O structures. It was observed that ester-type structures were rather prominent in LFER oils from New Albany shale. Thus.. the C=O bond stretching mode appeared at higher frequency indicating that the R group in the ester RCOOR’ was more alkyl than aryl in nature. R. The conversion of oil shales has been demonstrated to be an extremely rapid process. Hobbs. such as a Union B Retort. further work is required on gas and oil generation/separation to determine carbon distribution in char. J.. Shen et al. since the nitrogen gas was used as a secondary gas in these experimental tests. M.r.-S. the ester structures would be readily thermolysed.. 1991. For the beneficiated New Albany shale. Gaston. In the toluene extract of the New Albany spent shale.r. 1987. However. Rosencrans. of the 1985 Eastern Oil Shale Symposium’. of experimental results was in agreement with the model calculation results. L. This analysis provides a straightforward determination of the error limits on activation energy and bounds the activation energy whereas other approaches do not. The toluene extract was analysed using FT-i. However. DOE/METC-88/4080. If vaporization is a rate-controlling process. temperatures. especially with regard to the treatment of the particle size and shape determination. The fraction of asphaltenes in toluene solubles increased with temperature. ‘Proc.54. D. L. These observations demonstrated that the LFER pyrolysis liquid products had similar chemical character to asphaltenes (hexane insolubles). This may have resulted from reduced decarboxylation of the ester groups under higher heating rates that prevailed in the reactor. cr al. The relative concentration of C=O 2 3 FUEL. 1985 Shadle. For the New Albany shale. The weight loss data suggested that vaporization may play an important role in the initial stages of rapid devolatilzation. NTIS/DE88001077. ‘Flash Pyrolysis of Green River Shale’. the heat transfer and velocity calculations in the injection region of the reactor. November 1283 . It also provides a method for determining the fraction of each component in the reacting system in cases where the activation energy varies with conversion. the relationship between the log of the time required to reach a fixed level of conversion and the reciprocal temperature is used to determine the activation energy at that level of conversion. Shen. For a given residence time and temperature... R. This may be attributed to the higher (almost twice) organic oxygen content of New Albany shale than Colorado shale. different reaction models may be necessary to describe the rapid devolatilization of these two shales.6 s). D. REFERENCES 1 Shadle. The rate data for the raw shales indicated that eastern and western shales exhibited different reaction mechanisms: the conversion efficiency in the eastern shale depended strongly on heating rate while the western shale did not. the implications will be quite important in the design of processes in which shales of various grades are rapidly devolatilized. The model can accurately simulate the data for time dependence of conversion at a single temperature. Lexington. R. The ultimate organic conversion (or the maximum recoverable organic fraction in the shale studied) had to be varied for the different particle sizes and gas atmospheres.the maximum conversion had to be adjusted to match the experimental values for the different particle sizes or gas atmospheres. S. This was attributed to the formation of condensed and non-condensed polycyclic aromatic compounds from less complex aromatic compounds as the pyrolysis temperature increased. Vol 70. H. In addition. determination of the product yield. particle cluster formation in the reactor. the changes in the conversion rate. Chemical Industry Press.Kinetic studies of rapid pyrolysis: M. Technical Note. the relative amount of oils in toluene solubles increased with decreasing residence time. the fraction of oils in toluene solubles was in the order: Colorado shale > beneficiated New Albany > New Albany shale The oils from LFER samples were analysed by FT-i. G. CONCLUSIONS The techniques applied to investigate rapid oil shale pyrolysis have provided an insight into the reaction mechanisms. the relative aromatic concentration appeared to be high. The conversion of the beneficiated shale exhibited a greater temperature dependence than the feed shale. The model can account for the differences in the time-temperature profile and. L. The effect of particle size and heat transfer rates (using gases of different thermal conductivity) on rates and yields should be studied in more detail. of the International Conference on Oil Shale and Shale Oil’. 34 Liquid product composition Part of the pyrolysis products from LFER was retained on the spent shale. the relative concentration of the C=O bonds to aliphatic CHs increased with temperature. M. In a slow-heating-rate process. The LFER computer model was used to conduct a sensitivity analysis on particle size and gas atmosphere. Kinetic analysis of the data is being expanded to include an analysis of the shale conversion as a number of parallel first-order reactions in which the measured products are lumped together. Beijing. J. bonds to aliphatic CH groups did not change significantly with temperature. S.. gases and liquids. the weight loss rate predicted by the model was greater than that of experimental results. while Colorado shale oils contained a weak ester peak only at 850°C.. and this part was Soxhlet extracted with toluene. therefore. The maximum potential conversion obtained in helium or with the smaller particles was larger than that generated for 70 pm particles in nitrogen. M. J. In this method. et al. This suggests that the changes in heating conditions altered the extent of retrogressive reactions such that higher heating rates and mass transfer rates favoured higher conversion levels even at these short residence times (0. 1988 Shadle. and the overall activation energy can be estimated as a function of conversion”. The LFER experiments require further improvement. and Rosencrans. p. and separation of solids and vapours. Further validation of the particle trajectory model is desired and measurements of particle residence times. ‘Proc. velocities and size are required. Kentucky Center for Energy Research Laboratory. with maximum yields being achieved in < 1 s at temperatures near 800°C. and the results used to validate the heat transfer model.

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