No abstract

Smoldering combustion, the slow burning process associated typically with porous solids (e.g., charcoal), is here proposed as a novel remediation approach for nonaqueous phase liquids (NAPLs) embedded in porous media. Several one-dimensional vertical smoldering experiments are conducted on quartz sand containing fresh coal tar at an initial concentration of 71 000 mg/kg (approximately 25% saturation) and employing an upward darcy air flux of 4.25 cm/s. Following a short-duration energy input to achieve ignition at the lower boundary, a self-sustaining combustion front is observed to propagate upward at 1.3 x 10(-2) cm/s. The process is self-sustaining because the energy released during NAPL smoldering is efficiently trapped and recirculated by the soil matrix, preheating the NAPL ahead of the reaction front. The smoldering process is observed to self-terminate when all of the NAPL is destroyed or when the oxygen source is removed. Pre- and post-soil analysis revealed that NAPL smoldering reduced the concentration of total extractable petroleum hydrocarbons (TPH) from 38 000 mg/kg to below detection limits (< 0.1 mg/kg) throughout the majority of the column. A comparable experiment in which conductive heating is applied in the absence of smoldering demonstrates a 6-fold reduction in the net energy in the system and residual TPH values of 2000-35 000 mg/kg. A further repeat in which the air supply is prematurely terminated demonstrated that the NAPL smoldering process can be extinguished via external control. A suite of 23 demonstration experiments shows that NAPL smoldering is successful across a range of soil types (including simple layered systems) and contaminants (including laboratory mixtures of dodecane, DCA/ grease, TCE/oil, vegetable oil, crude oil, and mineral oil) as well as field-obtained samples of materials containing coal tar, oil drill cutting waste, and oil sands.

Smoldering combustion has been introduced recently as a potential remediation strategy for soil contaminated by nonaqueous phase liquids (NAPLs). Published proof-of-concept experiments demonstrated that the process can be self-sustaining (i.e., requires energy input only to start the process) and achieve essentially complete remediation of the contaminated soil. Those initial experiments indicated that the process may be applicable across a broad range of NAPLs and soils. This work presents the results of a series of bench-scale experiments that examine in detail the sensitivity of the process to a range of key parameters, including contaminant concentration, water saturation, soil type, and air flow rates for two contaminants, coal tar and crude oil. Smoldering combustion was observed to be self-sustaining in the range 28,400 to 142,000 mg/kg for coal tar and in the range 31,200 to 104,000 mg/kg for crude oil, for the base case air flux. The process remained self-sustaining and achieved effective remediation across a range of initial water concentrations (0 to 177,000 mg/kg water) despite extended ignition times and decreased temperatures and velocities of the reaction front. The process also exhibited self-sustaining and effective remediation behavior across a range of fine to coarse sand grain sizes up to a threshold maximum value between 6 mm and 10 mm. Propagation velocity is observed to be highly dependent on air flux, and smoldering was observed to be self-sustaining down to an air Darcy flux of at least 0.5 cm/s for both contaminants. The extent of remediation in these cases was determined to be at least 99.5% and 99.9% for crude oil and coal tar, respectively. Moreover, no physical evidence of contamination was detected in the treatment zone for any case where a self-sustaining reaction was achieved. Lateral heat losses to the external environment were observed to significantly affect the smoldering process at the bench scale, suggesting that the field-scale lower bounds on concentration and air flux and upper bound on grain size were not achieved; larger scale experiments and field trials where lateral heat losses are much less significant are necessary to define these process limits for the purposes of field application. This work provides valuable design data for pilot field trials of both in situ and ex situ smoldering remediation applications.

This paper presents a series of experiments conducted to assess the potential of smouldering combustion as a novel technology for remediation of contaminated land by water-immiscible organic compounds. The results from a detailed study of the conditions under which a smouldering reaction propagates in sand embedded with coal tar are presented. The objective of the study is to provide further understanding of the governing mechanisms of smouldering combustion of liquids in porous media. A small-scale apparatus consisting of a 100 mm in diameter quartz cylinder arranged in an upward configuration was used for the experiments. Thermocouple measurements and visible digital imaging served to track and characterize the ignition and propagation of the smouldering reaction. These two diagnostics are combined here to provide valuable information on the development of the reaction front. Post-treatment analyses of the sand were used to assess the amount of coal tar remaining in the soil. Experiments explored a range of inlet airflows and fuel concentrations. The smouldering ignition of coal tar was achieved for all the conditions presented here and self-sustained propagation was established after the igniter was turned off. It was found that the combustion is oxygen limited and peak temperatures in the range 800-1080 °C were observed. The peak temperature increased with the airflow at the lower range of flows but decreased with airflow at the higher range of flows. Higher airflows were found to produce faster propagation. Higher fuel concentrations were found to produce higher peak temperatures and slower propagation. The measured mass removal of coal tar was above 99% for sand obtained from the core and 98% for sand in the periphery of the apparatus