ENVIRONMENTAL ENGINEERING SCIENCE Volume 20, Number 2, 2003 Mary Ann Liebert, Inc.

Droplet Combustion of Chlorinated Benzenes, Alkanes, and Their Mixtures in a Dry Atmosphere
W.J. Stry,1 J.D. Felske,1 and N. Ashgriz2,*
1

Department of Mechanical and Aerospace Engineering State University of New York at Buffalo Amherst, NY 14260 2 Department of Mechanical and Industrial Engineering University of Toronto Toronto, ON, Canada, M5S 3G8

ABSTRACT Combustion of three chlorobenzenes (monochlorobenzene, dichlorobenzene, trichlorobenzene) and five alkanes (octane, decane, dodecane, tetradecane, and hexadecane) were investigated. Using high-speed video photography, the size and velocity of the burning drops at various points during their lifetime were measured. From such data, the time-variation of a droplets burning rate was deduced. It was found that the variations of the burning rates for the mixtures were qualitatively similar when viewed as functions of the chlorine to hydrogen atom ratio. Starting from a pure alkane, as Cl/H increased, the burning rate first decreased, then slightly increased, and then fell sharply near Cl/H 5 0.5 to approximately the vaporization rate of the pure chlorobenzene. It was also found that prior droplet combustion studies (performed in the H 2O-rich atmosphere of combustion-heated reactors) exhibited burning rates of the same liquid blends that were nearly twice the present dry atmosphere results. We have demonstrated that when the hydrogen in the surrounding atmospheric H2O is included in the ratio Cl/H, these previous results yield curves of burning rate vs. Cl/H that are similar to those of the present study. This implies that the enhanced burning rate observed when an alkane is blended into a pure chlorobenzene is partly due to the hydrogen provided by the alkane, and that a similar effect appears achievable by adding water vapor to the gas phase. Key words: droplet; combustion; chlorinated hydrocarbons

INTRODUCTION

the rate of generation of liquid hazardous wastes will probably increase. This is a result of three factors. First, the rate of produc-

OR THE FORESEEABLE FUTURE ,

tion of chemicals is increasing while the processes used to make them are remaining essentially the same thereby generating such wastes proportionally. Second, the number of substances that are classified as hazardous is continually increasing. Third, emission regulations for

* Corresponding author: Department of Mechanical & Industrial Engineering, 5 Kings College Road, University of Toronto, Toronto, Ontario M5S 3G8, Canada. Phone: 416-964-3407; Fax: 416-978-7753; E-mail: ashgriz@mie.utoronto.ca

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126 species presently defined as hazardous change as new scientific data are generated. Thus, even though incinerators may be operating within current regulations, they must be able to adapt to the burning of new materials and to new emission standards. In addition, potential restrictions on both the transportation of wastes and the siting/licensing of new hazardous waste incinerators may necessitate the use of on-site systems. The relatively short residence times associated with such smaller scale units will also contribute to the difficulty in achieving emission requirements. In view of these concerns, fundamental research into the physical processes of waste incineration is prudent. The two most prevalent types of hazardous waste incinerators are the rotary kiln and the liquid spray injector. It is the latter that motivates the present study. This paper discusses the burning characteristics of a category of hazardous/toxic liquids (chlorinated hydrocarbons; in particular, chlorinated benzenes), which are generated in large volumes each year by the petrochemical industry. These nonusable by-products are usually disposed of onsite by liquid spray incineration. Hence, applying the understanding gained by research of the type described herein will lead to important economic and environmental benefits for both industry and society alike.

STRY ET AL. burner. The fuels considered were pure alkanes, pure monochloroalkanes, and 1,1,2,2-tetrachloroethane(TECA). Their deduced burning rates exhibited sharp decreases as the chlorine to hydrogen mole ratio (Cl/H) approached unity. They found this difficult to explain. It is to be noted, however, that their calculation of (Cl/H) neglected the large amount of hydrogen contained in the water vapor of the postflame gases that heated and oxidized the droplets. In addition, they also reported the size and mass fraction histories plus the burning rates for mixtures of 85% (by volume) TECA-15% pure alkane. All data conformed to the d-squared law, and exhibited the trend that the less volatile the alkane, the higher the burning rate. This trend resulted from the less volatile alkane remaining in the droplet longerthereby enhancing the instantaneous rate of combustion for a greater period of time (TECA was the least volatile component in the mixtures). Chang et al. (1989) employed a postflat-flame combustion apparatus identical to that of Wang et al. (1984). Mixtures of pentachloroethane (PERC) and octane exhibited droplet burning behavior similar to the nonaneTECA mixtures of Sorbo et al. (1988, 1992). Average burning rates for droplets of pure chlorinated benzenes were found to be 0.90 mm2 /s for monochlorobenzene (MCB), 0.85 mm2 /s for 1,2-dichlorobenzene (DCB), and 0.78 mm2/s for 1,2,4-trichlorobenzene (TCB). Finally, Jackson et al. (1992) investigated the combustion of single droplets of heptane and its mixture with monochloroalkanes in a microgravity environment. They also showed that the burning rates of drops decreased as the number of carbon atoms per molecule increased. The purpose of the present study was to investigate the burning characteristics of liquid CHCs and their blends with alkanes in a dry atmosphere and compare the results with the presently available data obtained in the humid atmosphere of postflame gases. All of the liquids used for this study were 99% pure (HPLC grade). It is to be noted that these liquids are miscible with one another in all proportions.

PREVIOUS RESEARCH
In hazardous waste incineration, the principal organic hazardous components (POHCs) of the waste feedstock must be completely destroyed. To achieve these goals in liquid injection incinerators, the liquid must be properly atomized and efficiently mixed with the oxidizing environment. Also, sufficiently high combustion temperatures must be maintained throughout the residence time of the hazardous species inside the incinerator to enable complete vaporization and combustion of individual drops. Depending on the composition of the waste, conventional hydrocarbon fuel may be blended with it to raise the heat content of the liquid. Because the major components of liquid hazardous wastes are chlorinated hydrocarbons (CHCs), and because single droplet combustion plays an essential role in establishing various combustion regions within the complex sprays characteristic of industrial-scale burners, several fundamental studies of the physical processes of CHC droplet combustion have previously been performed. The most pertinent to the present discussion are briefly reviewed below. Sorbo et al. (1988) and Wang et al. (1984) investigated free-flowing droplet combustion in which single droplets were injected into the postflame gases of a flat flame

EXPERIMENTAL PROCEDURE Electrically heated combustion chamber

Most of the earlier free-flowing droplet experiments employed combustion chambers heated by burning premixed methane/air/oxygen. In many cases a porous plug burner was used (e.g., Sorbo et al., 1988); while others employed an array of bunsen-type burners (e.g., Gollahalli, 1979). In only one case known to us was electric heat employed (Bolt and Saad, 1956), but the design was problematic due to a cool region near the bottom of the chamber. Our ex-

COMBUSTION OF BENZENES IN A DRY ATMOSPHERE perience is that the porous plug, premixed gas chamber has a high temperature drop along its length, a significant level of radiative heat loss (due to the cool porous plug), and a long initial thermal transient (because it is relatively massive). Because of the many problems with gas heating, an electrically heated combustion chamber was designed and built for the present study. Figure 1 shows a schematic diagram of the combustion chamber. Two nickel alloy elements embedded in half-cylinder ceramic casings provide electric heat. These heaters are 76-cm long, with an inner diameter of 8.9 cm. To make room for windows, a gap of 2.5 cm was left between the half cylinders. Thus, the total hot volume is 6,450 cm3. The maximum operating temperature of the heaters is 1,475 K. The windows are high-purity quartz, fabricated in 2.54-cm squares and 0.318-cm thick. The windows sit on opposite sides of the chamber in pairs, thereby making it possible to see all the way through the chamber at each of 13 locations. (This arrangement facilitates back-lighting for photography). The maximum operating temperature for the windows is 1,270 K, which is the lowest of any chamber component. A support system allows the entire heater-insulation unit to be leveled.

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This is necessary to attain alignment of the windows with the gravitational axis, along which the droplets fall. Several types of insulation were used to cover and seal the heaters and also support the windows. Only the 26 window holes (1.3-cm diameter), the droplet entrance hole (0.5-cm diameter) at the top, and the two exhaust holes (0.6-cm diameter) at the bottom were not insulated. On startup, approximately 1 h is required to achieve a steady temperature near 1,200 K. Steady-state is maintained by switching the heaters on and off with two solidstate relays, regulated by a PID controller. This design produces excellent temperature uniformityless than 5 K variation from top to bottom at 1,194 K, the temperature used in almost all cases. The exhaust vacuum for the chamber was set by trial and error to achieve a level that approximately cancels the tendency of the flow to rise due to buoyancy. This keeps the mean ambient velocity of the chamber effectively zero compared to the velocity of the falling drop.

Droplet generator
An aerodynamic drop generator was designed and built for this experiment. It is a modified version of those used by others (e.g., Green et al., 1989), and is able to establish very stable trajectories of the drops as they leave the generator. The changes that were introduced along with a detailed description of its construction and performance are given by Stry (1992). The exit opening of the droplet generator is positioned 10 cm above the entrance hole of the combustion chamber. Across this distance, the drop accelerates due to gravity to at least 1 m/s. The position and orientation of the droplet generator require careful adjustment so that the droplets pass all 13 window pairs in locations where they can be easily back-lit and photographed. In addition, the initial droplet size must be such that the droplets ignite quickly, so that they are burning as they pass the windows and, ideally, completely burn out near the bottom window. The droplet generator was used to provide monosize drops in the range (550 to 650 mm, which would leave the generator with very low velocities at a frequency of approximately 3 per second. The resulting minimum droplet spacing was 0.3 m and the corresponding minimum value for the ratio of drop spacing to diameter was 460, which is several times greater than necessary to preclude dropletdroplet interactions.

Droplet size vs. position

Figure 1. The electrically heated combustion apparatus. The internal hot chamber (dashed lined) is cylindrical with 10-cm diameter and 76-cm length.

A high-speed video camera and its spark source strobe light (Kodak Ektapro 1000) were positioned adjacent to a given window pair and were used to photograph the ENVIRON ENG SCI, VOL. 20, NO. 2, 2003

128 passing droplets. The vertical location of the camera was measured at every window, using the base of the optical stand as a fixed reference. A focusing bellows and 135mm lens were used and resulted in a resolution of 19 mm per screen pixel. The useful range of droplet diameters on the display screen was therefore from 5 to 35 pixels. Size measurements were made at the relatively low framing rate of 60 per second to achieve a large exposure time. This enabled the use of a small aperture, and thereby resulted in the sharpest possible focus. The size of a droplet was measured with a digital reticle from the video frame upon which it appeared.

STRY ET AL. where f is the fuel to oxygen mass ratio, YO 2,` the mass fraction of oxygen in the air; DHT ` the heat of combustion evaluated at the ambient temperature, T` ; cp the specific heat of the fuel vapor evaluated at the mean of Tf and the boiling point of the fuel, Tb ; and L is the enthalpy of vaporization at Tb . Fitting an nth order polynomial to the measured Re1/2(t) values, Re1/2(t) 5

n5 0

an 1 1 tn

(4)

Droplet velocity vs. position

Velocity measurements require consecutive observations of a single droplet, and therefore, the camera was run at 1,000 frames per second. Although this compromised focus, focus is much less critical for the velocity measurements because the screen lengths involved are normally well over 100 pixels.

allows integration of d[d2 (t)]/dt 5 2k(t) 5 Equation (1). The resulting time-dependence of the droplet size is given by: d 2 5 do 2 2 ko t 1 0.276 Pr1/3

N1 1

n ^ }} n5 1 n

tn

(5)

DATA REDUCTION
The objective is to determine the droplet size as a function of time. The size was always measured directly. The time was determined by fitting a polynomial to the measured 1/V(x) 5 dt/dx, where x 5 0 at the top of the combustion chamber and increases downward. Integration of this polynomial yields the function t(x), which is the time a droplet has spent in the hot chamber when it arrives at position x. Because a difference in velocity exists between the droplet and the gas in the combustion chamber, forced convection will influence the burning of the drop. Hence, the burning rate will depend upon the droplet Reynolds number, Re, and the gas phase Prandtl number, Pr. The droplet Reynolds number is defined as Re ; Vd/n, where V is the droplet velocity relative to the surrounding gas, d is the droplet diameter, and n is the kinematic viscosity. Ranz and Marshall (1952) proposed the following empirical correlation to account for the convective effect: k(t) 5 ko [1.0 1 0.276 Pr1/3Re1/2(t)] (1)

where do is the droplet diameter at t 5 0. The quantity in parentheses in Equation (5) will be called the convection modified time, t. A plot of d 2 vs. t yields a straight line of slope ko. Values of ko found from the data by linear regression using Equation 5 will be called the convection modified burning rates.

RESULTS
The droplet size histories for all of the liquids tested are given in Stry (1992). Also given there are the Reynolds number histories, the velocity vs. position data, and the position vs. time data. The accuracy with which

where the burning rate, k(t), is the instantaneous slope of the d 2 vs. t curve, ko is the constant slope for the same fuel corresponding to zero relative velocity, and is given by: 8 l ko 5 } } } } ln(1 1 B) rl cp B ; [f YO 2,` DH T` 1 cp (T` 2 Tb)]/ L (2)
Figure 2. Variation of the convection modified burning rate with amount of monochlorobenzene for various alkane mixtures.

in which B is the dimensionless transfer number defined as: (3)

COMBUSTION OF BENZENES IN A DRY ATMOSPHERE the convection modified burning rates were determined was conservatively estimated to be within 60.03 mm2 /s. This uncertainty was primarily determined by comparing the results of independent tests conducted on identical liquids. Also, the measured burning rates for the six pure alkanes tested here were all within 0.03 of the accepted value of 0.9 mm2 /s. Figure 2 shows a plot of the convection modified burning rate vs. the mol fraction (X) of MCB in decane, dodecane, and hexadecane. The curve sketched through the data are flat for small amounts of MCB and then bend downwards. However, because the difference in burning rates between the pure MCB and the pure alkane is only about three times greater than the absolute value of the measurement error, it is not possible to establish an accurate variation for the burning rates of intermediate mixtures. Although not tested in this study, the burning rate for benzene from the suspended fiber experiments of Godsave (1953) is practically identical to that of the alkanes. The present measurements yielded a burning rate for MCB close to that of the alkanes and, therefore, close to that of benzene. This is similar to the result of Sorbo et al. (1988), in that monochloroalkanes burn at nearly the same rate as the corresponding pure alkanes. Evidently, one chlorine atom substitution is not enough to significantly alter the physics of droplet burning for either chain or ring hydrocarbon liquids. Figure 3 shows three curves; the upper one is the same as the dodecane curve of Fig. 2, and the other two are analogous results for DCBdodecane and TCBdodecane mixtures. Unlike the data in Fig. 2, the range of burning rates covered in Fig. 3 is more than 20 times the absolute

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value of the measurement error. Thus, meaningful trends are clearly established. The latter two curves have similar shapes. From left to right, an initial decrease in burning rate is followed by a minimum and then a slight increase; then a region of nearly constant burning rate occurs followed finally by a sharp decrease. The TCB curve flattens out again once XTCB . 0.9. At these concentrations the drops are not burning (i.e., no flame is visible at 1,194 K); instead, they are simply vaporizing. Thus, a vaporization rate of about 0.4 mm2/s serves as a lower limit to the measured burning rates. Figure 4 shows the burning rates for various DCB alkane mixtures. As in the case of MCB, the burning rates of the blends fall between the extremes of a pure alkane and a pure chlorinated benzene. The nonlinear dependence on the mixture fraction is similar to the results of Sorbo et al. (1988) and Chang et al. (1989). In Fig. 4, all the results except octane fall very close to a single curve. The lower burning rates exhibited by the DCBoctane mixtures are the result of two-stage burning. This was deduced from plots of d 2 vs. t, such as the one given in Fig. 5. The first stage has a slope of 20.81 mm2/s, which is close to the value for the less volatile alkanes at the same mole fraction. (All plots of d 2 vs. time for alkanes were linear after a liquid heating period.) The second stage slope is 20.43 mm2/s, which is the same as that of the pure DCB. Clearly, all the octane in the mixture is depleted during the first stage and only DCB remains during the second stage. The abruptness of the transition indicates that the droplet is well mixed during the initial stage. The burning rates for TCBalkane mixtures are shown

Figure 3. Variation in burning rate with mixture ratio for several chlorinated benzenes with dodecane.

Figure 4. Burning rates for dichlorobenzene mixtures with various alkanes.

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STRY ET AL. alkane fuel had a significantly lower boiling point than the chlorinated benzene. The systems that had two-stage burning were octaneDCB, octaneTCB, and decane TCB, with boiling temperatures of 399 for octane, 447 for decane, 452 for DCB, and 487 for TCB. Thus, there was at least a 40 K difference in boiling points. For the reverse situation, such as the MCBhexadecane mixtures, this phenomenon was not observed. Only when the more vigorously burning fuel was also the more volatile fuel did two-stage burning occur. Furthermore, the mixtures involving a less volatile alkane show single linear d 2 vs. t behavior because even though the alkane concentration in the droplet is increasing with time, the effect on the burning rate is small. This can be surmised from Figs. 4 and 6, which show that major burning rate changes only occur at low alkane concentrations. The theoretical burning rates computed from Equation (1) were compared to the measured values for the MCBand DCB-based blends. (A comparison for TCB and its blends was not made due to a lack of property values.) For MCB, Equation (1) was found to be fairly accurate except at very high concentrations of MCB. For pure MCB, the prediction was high by more than 10%. For DCB, the theoretical predictions were quite poor at high concentrations of DCB, with pure DCB overestimated by more than a factor of 2. Although the material property values are uncertain (particularly the fuel vapor thermal conductivity), this cannot explain errors of this magnitude. The chlorine to hydrogen atom ratio, Cl/H, had been identified as an important parameter in earlier studies (Bose and Senkan, 1983; Chelliah et al., 1991). The difference between theory and measurement as a function of this ratio was found to increase with Cl/H. The relationship of burning rate to Cl/H was determined to be approximately linear, with MCB and DCB having different slopes. For Cl/H . 0.1, reasonable burning rates are predicted by Equation (1). However, Equation (1) does not do well for MCB mixtures outside this range, even at fairly low values of Cl/H. One possible reason is that soot escapes the flame zone under these conditions, and it may carry with it a significant amount of the total available chemical energy. Because the predictions made by Equation (1) are quite poor for all cases when Cl/H is moderately large, some inconsistency must exist between its underlying assumptions and the actual physics of the burning process. Although not observed in this study, others report extinction of drops for highly chlorinated liquids, including one observation for TCB (Chang et al., 1989). In the present study, pure TCB shows no visible flame in 1,194 K air and only a faint glow in 1,265 K air. Extinction and nonignition phenomena imply that the chemical reaction time

Figure 5. Convection modified size history for a dichlorobenzeneoctane mixture that shows two-stage burning. The lower slope is nearly identical to that measured for pure dichlorobenzene.

t indicate that twoin Fig. 6. Detailed plots of d 2 vs. stage burning occurs for TCBdecane, similar to DCBoctane (see Stry, 1992). For XTCB 5 0.79, the first stage slope (20.72 mm2 /s) is close to that of the less volatile alkanes at the same mole fraction, and the second stage slope (20.39 mm2 /s) is approximately the value of pure TCB. For the cases that exhibited two-stage burning, the

Figure 6. Burning rates for trichlorobenzene mixtures with various alkanes.

COMBUSTION OF BENZENES IN A DRY ATMOSPHERE scales are of the same order of magnitude as the diffusive transport time scales (i.e., the Damkhler number is near unity). Thus, the probable reason for failure of Equation (1) is that there exists enough chlorine to sufficiently retard the chemical reactions so as to invalidate the quasisteady assumption upon which this equation is based. In addition, as noted by Stry (1992), the variations of Cl/H with mole fraction for several binary systems changes rapidly at roughly the same mole fractions where rapid changes in burning rates are observed. Figure 7 shows data from the DCBdodecane, TCB dodecane, and TECAnonane systems plotted against Cl/H, where the amount of H includes a contribution from the surrounding hot gases. This Cl/H is different from that used by Sorbo et al. (1992) and others (Chang et al., 1989). In these prior experiments, droplet burning occurred in the postcombustion gases of a flat flame burner. Consequently, the hot surrounding atmosphere contained substantial amounts of H2O. Bose and Senkan (1983) have pointed out that the thermodynamics of the Deacon reaction 1 2HCl 1 } } O2 5 H2 O 1 Cl2 2 (7)

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strongly favors conversion of water to HCl at flame temperatures. Thus, the hydrogen atoms contained in the water vapor of the surrounding atmosphere are chemically active and should be included in the ratio Cl/H. The outstanding characteristic of all three curves in Fig. 7 is the sharp reduction in burning rate near similar

Figure 7. Variation of the burning rate with Cl/H for several chlorinated hydrocarbonalkane systems. 1,1,2,2-Tetrachloroethanenonane results are from Sorbo et al. (1988). Because the water vapor in their postflame combustion chamber is accounted for, the pure dichlorobenzene and trichlorobenzene results from Chang et al. (1989) have different Cl/H than the present study.

values of Cl/H. For Cl/H 5 0.5, the burning rates are essentially equal to the pure vaporization rate of the chlorinated benzene, indicating that combustion has ceased. (The TECAnonane vaporization is higher because of a 200 K hotter atmosphere; also, the data were not modified for convection.) The results of Chang et al. (1989) for pure DCB and pure TCB use a definition for the ratio Cl/H that differs from the Cl/H for pure DCB and pure TCB in the present study in that they neglected the effect of hot water vapor in the atmosphere of their experiments. The open triangles represent convection-modified rates evaluated from their nonmodified results using 1,900 K as the property reference temperature. These points fall very close to the curves of the present study, despite the fact that in the former case the only source of additional hydrogen was the H2O in the surrounding atmosphere while in the present study the only source of additional hydrogen was the alkane blended into the chlorobenzene. These observations lead to the important conclusion that the sharp increase in burning rate upon adding small amounts of alkanes to dichlorobenzene and trichlorobenzene results from the contribution of hydrogen and not from an increased heat of combustion. Furthermore, once there is enough hydrogen to overcome chlorine radical scavenging, further additions have little effect. This is why adding small amounts of alkanes to chlorinated compounds causes dramatic increases in the burning rate, whereas adding larger amounts produces only modest additional benefit (as seen in Figs. 4 and 6). When the data for the DCBdodecane, TCBdodecane, and TECAnonane systems are plotted against Cl/H computed by neglecting any atmospheric hydrogen atoms contained in H2 O, the abrupt change in burning rate for the blends occurs at quite different Cl/H. Also, the pure DCB and pure TCB results differ by a factor of 2. In contrast to this disparate behavior, Fig. 7 demonstrates that accounting for hot atmospheric water vapor leads to data that follow simpler and more consistent trends. Attempts were made to correlate the burning behavior with a single parameter. Several different parameters were tried. The one that results in the best correlation of the burning rates for Cl/H , 0.3 was the ratio of the heat of combustion to the heat of vaporization, H c /L. (The value Cl/H 5 0.3 was selected arbitrarily, noting simply that above this value the burning rate decreases rapidly.) This correlation is presented in Fig. 8, where it is seen that almost all of the data lie within the range of error of the measurements. The exceptions are mixtures of TCB having high alkane concentrationstheir burning rates being lower than expected. The following equation is offered as a correlation for the convection-modified droplet ENVIRON ENG SCI, VOL. 20, NO. 2, 2003

132 burning rates of chlorinated benzene and alkane blends with Cl/H , 0.3: ko 5 0.24 1 9.5 3 102 3 (Hc /L) 2 34 3 102 6 (Hc /L)2 (8) It is interesting that Hc /L correlates the data better than the parameter (8l/rlcp )ln(1 1 B). One possible reason is the appearance of the fuel to oxygen mass ratio, f, in the dimensionless transfer number, B. The large contribution of chlorine to the mass of chlorinated benzene blends causes their values for f, and hence (8l/rlcp )ln(1 1 B), to be much larger than for plain alkanes. However, because the chlorine forms HCl, it is never involved with oxygen, and therefore, the predicted strong increase with f does not occur.

STRY ET AL. Plots of burning rate vs. Cl/H for several chlorinatedbenzene/alkane systems show similar behavior. As Cl/H increases from zero, the burning rate first decreases, then increases, and finally decreases sharply to a limiting value equal to the vaporization rate of the pure chlorinated species. For chlorinated benzene/alkane mixtures, the final sharp decrease occurs for Cl/H near 0.5. Results from an earlier study of the 1,1,2,2-tetrachloroethane nonane system exhibit a nearly identical behavior if the originally defined Cl/H is modified to include the hydrogen atoms contained in the hot water vapor of the atmosphere that was employed. The detrimental effect of chlorine is due to radical scavenging that markedly increases the characteristic chemical reaction time and therefore lowers the Damkhler number. Burning rates predicted by diffusion flame theory agree with the measured convection modified burning rates only when Cl/H , 0.1. For larger Cl/H, this theory overestimates the burning rate. The difference between predicted and measured values increases linearly with Cl/H. For pure DCB, with Cl/H near 0.5, the predicted burning rate of 1.05 mm2/s is more than twice the measured value of 0.43 mm2 /s. Diffusion flame theory fails because chlorine radical scavenging slows reaction rates enough to invalidate the assumption that all of the chemical energy released is available to assist gasification. For Cl/H up to about 0.3, burning rates follow a single quadratic curve [Equation (8)] in terms of the dimensionless parameter Hc /L. For larger values of Cl/H, the inhibiting effects of chlorine dominate, and the burning rate falls sharply. Further investigation of the addition of hot water vapor to the atmosphere surrounding burning droplets of chlorinated hydrocarbons would help to corroborate the

CONCLUSIONS
The primary reason that alkane addition to chlorobenzenes increases their burning rates seems to be because of the hydrogen supplied. Earlier measurements of the burning rates of 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, in which additional hydrogen was supplied by H2O in the surrounding hot atmosphere, exhibit burning rates that are the same as those presently measured, in which hydrogen was supplied only by blending an alkane with the chlorinated benzene. Once sufficient hydrogen is present to overcome the effects of chlorine radical scavenging, further additions have little influence. This is why adding small amounts of alkanes to DCB and TCB cause dramatic increases in their burning rates while adding larger amounts produce only modest additional benefit.

Figure 8. Burning rates from the present study plotted against the ratio of the heat of combustion to the heat of vaporization. Two-stage burning liquids and liquids with Cl/H . 0.3 are not included.

COMBUSTION OF BENZENES IN A DRY ATMOSPHERE strong positive influence on burning rates which was inferred to occur from the present research. If found to be generally true, then the use of steam addition to an incinerator dedicated to the combustion of such liquids could provide a relatively inexpensive means for augmenting its combustion efficiency. In addition, the potential would also exist for transforming a greater percentage of the chlorine to HClthereby reducing the amount of Cl available in the exhaust gases where lowtemperature, catalytic reactions may consume it, producing dioxins or furans.

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GODSAVE, G.A.E. (1953). Studies of the combustion of fuel drops in a fuel spraythe burning of single drops of fuel. Fourth Symposium (International) on Combustion, The Combustion Institute, pp. 819830. GOLLAHALLI, S.R. (1979). An experimental study of the combustion of the unsupported drops of residual oils and emulsions. Combust. Sci. Technol. 19, 245250. GREEN, G.J., TAKAHASHI, F., WALSH, D.E., and DRYER, F.L. (1989). Aerodynamic device for generating monodisperse fuel droplets. Rev. Sci. Instrum. 60, 646652. JACKSON, G.S., AVEDISIAN, C.T., and YANG, J.C. (1992). Observations of soot during droplet combustion at low gravity: Heptane and heptane/monochloroalkane mixtures, Int. J. Heat Mass Transfer 35(8), 20172033. RANZ, W.E., and MARSHALL, W.R., Jr. (1952). Evaporation from drops. Chem. Eng. Prog. 48, 141180. SORBO, N.W., and CHANG, D.P.Y. (1992). Observations of chlorinated-hydrocarbon droplet gasification. Combust. Sci. Technol. 85(16), 419435. SORBO, N.W., LAW, C.K., and CHANG, D.P.Y. (1988). An experimental investigation of the incineration and incinerability of chlorinated alkane droplets. Twenty-Second Symposium (International) on Combustion. The Combustion Institute, pp. 20192026. STRY, W.J. (1992). The combustion of free flowing droplets of chlorinated benzenes, alkanes, and their mixtures. PhD thesis, State University of New York at Buffalo. WANG, C.H., LIU, X.Q., and LAW, C.K. (1984). Combustion and microexplosion of freely falling multicomponent droplets. Combust. Flame 56, 175197.

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BOLT, J.A., and SAAD, M.A. (1956). Combustion rates of freely falling fuel drops in a hot atmosphere. Sixth Symposium (International) on Combustion, The Combustion Institute, pp. 717725. BOSE, D., and SENKAN, S.M. (1983). On the combustion of chlorinated hydrocarbons: I. Trichloroethylene. Combust. Sci. Technol. 35, 187202. CHANG, D.P., SORBO, N.W., LAW, C.K., STEEPER, R.R., RICHARDS, M.K., and HUFFMAN, G.L. (1989). Relationships between laboratory and pilot-scale combustion of some chlorinated hydrocarbons. Environ. Prog. 3, 152162. CHELLIAH, H.K., LAW, C.K., and SORBO, N. (1991). A simplified model for the diffusional burning of mixtures of chlorinated hydrocarbons. In: Heat and Mass Transfer in Fire and Combustion Systems, Atlanta, GA, December 1991, ASME, pp. 4956.

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