Materials and energy recovery from oily sludges removed from crude oil storage tanks (tank bottoms): A review of technologies.

Sludge and solids accumulating in crude oil storage tanks (referred as tank bottoms) reduces tank volume and requires periodic removal and disposal. Effective management of tank bottoms require considerations to reduce the toxicity of wastes and reduce potential environment impacts. This review compares alternative technologies for economical and environmentally beneficial management of oily sludges for recovery of hydrocarbons and energy with and without oil recovery. Management options with oil recovery include solvent extraction, centrifugation, surfactant oil recovery, and pyrolysis. Management options without oil recovery include incineration and anaerobic co-digestion. The selection of the appropriate technology depends on the characteristics of oily sludge, treatment capacity, as well as operation and maintenance costs. An efficient treatment can involve integration of different technologies for recovery of different oil fractions and to reduce energy demand. Technologies that utilize renewable energy (e.g., solar pyrolysis) can offset the high energy demand of pyrolysis process while recovering marketable products.

Removal of crude oil from highly contaminated natural surfaces with corexit dispersants.

Dispersants are used to reduce the impact of oil spills in marine environment. Experiments were conducted with natural materials which were contaminated by direct application of fresh Louisiana crude oil. The natural materials evaluated included sea sand (South Beach in Miami, Florida), red mangrove leaves (Rhizophora mangle), and sea shells (Donax variabili). Salt water at two different salinities (17 and 34 ppt) was used with two types of Corexit dispersant solutions (9500A and 9527A) in concentrations ranging from 100 to 3500 mg/L. Washing of the contaminated samples was conducted by a three-step mixing procedure (salt water only, then with the addition of the dispersant solution to the salt water, and salt water) to simulate oil-saltwater-dispersant interactions. In general, increasing dispersant concentration increased the percentage of oil dispersed into the aqueous phase up to dispersant solutions containing 400 mg/L for Corexit 9500A and 300 mg/L Corexit 9527A. Increasing the dispersant concentration above these levels also decreased the dispersion of oil from the surfaces. At very high concentrations of dispersant solutions (above 1500 mg/L), the percentage of oil dispersed into the solution from the contaminated surfaces was about one half what was observed at 400 mg/L with Corexit 9500A and 300 mg/L Corexit 9527A. Although dispersants were most effective for removing the fresh Louisiana crude oil from sand particles and dispersing into the solution due to large surface area of the particles per unit weight; the residual oil remaining on the sand particles was relatively high in comparison to mangrove leaves and sea shells due to clustering of sand particle with oil. There was some oil penetration into the porous structure of the sea shells (at the microscopic level) which could not be removed.

Struvite formation and decomposition characteristics for ammonia and phosphorus recovery: A review of magnesium-ammonia-phosphate interactions.

Struvite (MgNH4PO4·6H2O) forms in aqueous systems with high ammonia and phosphate concentrations. However, conditions that result into struvite formation are highly dependent on the ionic compositions, temperature, pH, and ion speciation characteristics. The primary ions involved in struvite formation have complex interactions and can form different crystals depending on the ionic levels, pH and temperature. Struvite as well as struvite analogues (with substitution of monovalent cations for NH4+ or divalent cations for Mg2+) as well as other crystals can form simultaneously and result in changes in crystal morphology during crystal growth. This review provides the results from experimental and theoretical studies on struvite formation and decomposition studies. Characteristics of NH4+ or divalent cations for Mg2+ were evaluated in comparison to monovalent and divalent ions for formation of struvite and its analogues. Struvite crystals forming in wastewater systems are likely to contain crystals other than struvite due to ionic interactions, pH changes, temperature effects and clustering of ions during nucleation and crystal growth. Decomposition of struvite occurs following a series of reactions depending on the rate of heating, temperature and availability of water during heating.

Gravity induced densification of floating crude oil by granular materials: Effect of particle size and surface morphology.

Densification and sedimentation of floating crude oil to the bottom of water column reduces the radius of a spill and its mobility, preventing direct contamination of beaches, coastal flora and fauna. Performances of different natural granular materials were evaluated for capturing efficiency of floating fresh South Louisiana crude oil. The granular materials studied were quartz sand with medium (20-30mesh) and fine (40-100mesh) particle size, limestone with coarse (4-10mesh) and medium (16-40mesh) particle size, beach sand (20-80mesh), and clay (kaolin with ferric oxide; passing 200mesh). Beach sand (mixture of quartz and limestone 20-80mesh) and limestone (16-40mesh) demonstrated better performance for capture, densification and submergence of the crude oil among the materials evaluated. The behavior of granular particles with the hydrophobic phase can be classified as (1) immersion entrapment inside the hydrophobic phase (slurry), and (2) partial encapsulation of the hydrophobic phase by a single layer of particles (raft). With crude oil, the particles were primarily entrapped within the hydrophobic phase. Study of the effect of particle size and morphology (i.e., porosity) of the granular materials on capture performance showed that average surface pore size did not have a significant effect on aggregation with oil, however, higher capture efficiency was observed with materials of higher surface porosity (beach sand and limestone). The experiments revealed that there is a critical particle size range (passing 10mesh) which resulted in more effective aggregation of the granular materials with crude oil.

Partitioning of fresh crude oil between floating, dispersed and sediment phases: Effect of exposure order to dispersant and granular materials.

When three or more high and low energy substrates are mixed, wetting order can significantly affect the behavior of the mixture. We analyzed the phase distribution of fresh floating Louisiana crude oil into dispersed, settled and floating phases depending on the exposure sequence to Corexit 9500A (dispersant) and granular materials. In the experiments artificial sea water at salinity 34‰ was used. Limestone (2.00-0.300 mm) and quartz sand (0.300-0.075 mm) were used as the natural granular materials. Dispersant Corexit 9500A increased the amount of dispersed oil up to 33.76 ± 7.04%. Addition of granular materials after the dispersant increased dispersion of oil to 47.96 ± 1.96%. When solid particles were applied on the floating oil before the dispersant, oil was captured as oil-particle aggregates and removed from the floating layer. However, dispersant addition led to partial release of the captured oil, removing it from the aggregated form to the dispersed and floating phases. There was no visible oil aggregation with the granular materials when quartz or limestone was at the bottom of the flask before the addition of oil and dispersant. The results show that granular materials can be effective when applied from the surface for aggregating or dispersing oil. However, the granular materials in the sediments are not effective neither for aggregating nor dispersing floating oil.

Granular encapsulation of light hydrophobic liquids (LHL) in LHL-salt water systems: Particle induced densification with quartz sand.

Addition of granular materials to floating crude oil slicks can be effective in capturing and densifying the floating hydrophobic phase, which settles by gravity. Interaction of light hydrophobic liquids (LHL) with quartz sand was investigated in LHL-salt water systems. The LHLs studied were decane, tetradecane, hexadecane, benzene, toluene, ethylbenzene, m-xylene, and 2-cholorotoluene. Experiments were conducted with fine quartz sand (passing sieve No. 40 with openings 0.425 mm). Each LHL was dyed with few crystals of Sudan IV dye for ease of visual observation. A volume of 0.5 mL of each LHL was added to 100 mL salt water (34 g/L). Addition of one gram of quartz sand to the floating hydrophobic liquid layer resulted in formation of sand-encapsulated globules, which settled due to increased density. All LHLs (except for a few globules of decane) formed globules covered with fine sand particles that were heavy enough to settle by gravity. The encapsulated globules were stable and retained their shape upon settling. Polarity of hydrophobic liquids as the main factor of aggregation with minerals was found to be insufficient to explain LHL aggregation with sand. Contact angle measurements were made by submerging a large quartz crystal with the LHL drop on its surface into salt water. A positive correlation was observed between the wetting angle of LHL and the LHL volume captured (r = 0.75). The dependence of the globule density on globule radius was analyzed in relation to the coverage (%) of globule surface (LHL-salt water interface) by fine quartz particles.

Decrease in osmotically driven water flux and transport through mangrove roots after oil spills in the presence and absence of dispersants.

The objective of this study was to evaluate the effect of crude oil on water transport through mangroves roots in the presence and absence of dispersants. Water transport through the roots were evaluated experimentally using red mangrove root segments exposed to salt water contaminated with Louisiana crude oil for seven days in the presence and absence of Corexit 9500A (dispersant). Experimental observations were interpreted in view of the structural integrity and fouling phenomena observed on the epidermis and endodermis layers of the roots. The effects of oil on the radial water flux through the epidermis and endodermis were analyzed using a dual layer filtration model. Progression of fouling due to accumulation and penetration of the contaminants through the root layers were interpreted in relation to observed mangrove health (long and short term effects) reported in the literature.

Instantaneous stabilization of floating oils by surface application of natural granular materials (beach sand and limestone).

When granular materials are applied to hydrophobic liquids floating over another liquid (i.e., water), particles form aggregates which can be separated from the floating phase. This concept can be used for controlling mobility of floating oils, especially after oil spills near coastal areas. The objectives of this research were to characterize oil capture efficiency and determine effectiveness of particles for converting the floating phase to a heavier phase for effective separation. Experiments were conducted with South Louisiana crude oil contaminated salt water, limestone and quartz sand. Although the oil removal efficiency increased with the increasing amount of granular material applied, it did not increase linearly. About 50% of the floating oil was removed by aggregates, regardless of the material used, when granular material to floating oil ratio was about 1 g/g. The aggregates separated had higher amounts of oil content when smaller amounts of granular materials were added.

Removal of emulsified fuel oils from brackish and pond water by dissolved air flotation with and without polyelectrolyte use: pilot-scale investigation for estuarine and near shore applications.

In coastal areas, estuaries, and inland waters, dispersant use after oil spills is not allowed due to sensitivity of the ecosystems. The purpose of this study was to investigate the removal of emulsified fuel oils from brackish and pond water by dissolved air flotation (DAF) with and without use of coagulants. Experiments were conducted with a 60L DAF system. Fuel oil-water emulsions were prepared with regular unleaded gasoline, jet fuel, and diesel fuel mixed at 1:1:1 (v/v/v) ratio. Batch and continuous runs were conducted at air pressurization of 354.6kPa. During both batch and continuous modes, significant petroleum hydrocarbon (PHC) removal was achieved within 10 min. Coagulant addition initially increased the PHC removal by about 5-15%. However, effectiveness of the coagulant was not significant after 20 min due to breakage of the aggregates. In general, the pond water had higher PHC removal than the brackish water. With longer run times, PHC removal improved slightly and the effluent contained increasing fractions of higher molecular weight compounds indicating that PHC removal was due to both DAF and stripping processes. Results indicate that DAF process can be effective both with and without the use of coagulants for removing PHCs from brackish and pond waters.