Petrotech 2001 Conference, Bahrain 29-31 October 2001

PN#200 Reactor-Based Process for the Biological Treatment of Petroleum Wastes

Ajay Singh*, Bill Mullin and Owen Ward Petrozyme Technologies Inc., 7496 Wellington Road 34, R.R. # 3, Guelph, Ontario, Canada N1H 6H9

ABSTRACT A bioreactor-based process has been developed for the treatment of oily sludges generated from exploration, production and refining of oil. The keys to the process are optimized nutrient and other culture conditions designed to increase hydrocarbon bioavailabilty and promote high growth rates of a hydrocarbondegrading mixed indigenous bacterial culture possessing the necessary diverse metabolic capability. A decrease in the toxic mobile organic compounds to nonhazardous levels is achieved in 6-10 days. In locations where landfarming is permitted, treatment with the Petrozyme Process can reduce the land area needed to apply the sludge by up to 80%. On an existing landfarm, the biodegradation efficiency of any undegraded hydrocarbons from prior sludge applications is further improved. Where landfarming is not allowed, the treated solids may be separated for industrial reuse or disposal in a non-hazardous landfill. Other benefits of the process include modular components, equipment simplicity and mobility, high biodegradation rates, robustness to variations in petroleum sludge composition and ease of operation. The process has been successfully demonstrated at pilot- and full-scale in various petroleum refineries

in Canada, the United States, Venezuela and Mexico and is currently in commercial operation in the United States and Venezuela.

INTRODUCTION The exploration, production, refining and distribution of petroleum and petrochemical products results in the generation of a considerable volume of waste oil sludges. These sludges come from a variety of sources including storage tank bottoms, oil-water separators, dissolved air floatation units, cleaning of processing equipment, biological sludges from waste water treatment units and oil spills in the oil fields, drilling sites and refineries (Manning and Thompson 1995). The composition of sludges varies with their origin and storage conditions but might typically contain up to 10-30% hydrocarbons, 5-20% solids and the remainder water (Speight 1991). Chemical composition of a variety of petroleum sludges is shown in Table 1. A variety of physical, chemical and biological approaches have been taken to remediating refinery sludges. In many countries these sludges have been accumulated in large lagoons, facilitating some recycling of oil but requiring later remediation of residual oily sludges. Attempts to process these sludges using centrifugal methods to separate oil, water and solids phases is highly capital intensive, is not consistently effective and still produces residual solids with high petroleum hydrocarbon content. Another option is to direct oily sludge waste to a delayed coker, however, this can degrade the sludge quality and reduce its economic value. Foul odors

are often reported in the coke product after sludge injection and can result in operator complaints. Sludge injection requires modifications to the coker as well as pretreatment of the sludge. This pretreatment step requires the use of milling, filtering and centrifugation equipment and a skilled operator. Thermal desorbers and incinerators have been used for the treatment of oily sludges. However, most of the above methods are capital intensive and therefore are associated with overall high sludge treatment costs.

Biological treatment of oily sludges The use of biological processing to treat waste or waste contaminated material is well-documented (Prince 1993; Atlas and Cerniglia 1995). Bioprocessing involves exploiting abilities of indigenous or augmented microorganisms to metabolize organic substrates (Ward 1991). It can be accomplished in a land-based environment (landfarming, composting or biopiling) or in some cases

bioremediation may be carried out in situ by enhancing microbial degradation of contaminants in the subsurface of soil. In other cases, contaminated material may be treated in slurry bioreactors to degrade petroleum hydrocarbons. The process of landfarming has been implemented worldwide as a means of biological treatment and disposal of oily sludges (Huesemann 1994). The sludges are sprayed on land together with fertilizers and the soil is tilled to promote the activity of natural soil microbial population for the degradation of petroleum hydrocarbons. Although landfarming may be a low cost method if land is available, it requires very long treatment times due to lack of control on

environmental factors such as seasonal variation in temperature, pH, moisture, and natural microbial activity, mixing and circulation limitations (Boopathy 2000). In climates with limited rainfall, the cost to maintain the proper moisture content in the soil could be prohibitive. Lack of uniformity causes high contaminant concentration/toxicity in localized pockets and inconsistent permeability of soil makes it difficult to apply treatment additives like nutrients and oxygen (Devinny and Islander 1989). Care also needs to be taken to ensure that landfarms are isolated from watercourses. Most of the above limiting factors are eliminated in employing bioreactor technology. It eliminates the need to spray high concentrations of petroleum hydrocarbons on large areas of land. The bioreactor-based process is characterized by much higher rates and extents of degradation than are observed in landfarming systems due to the minimization of mass-transfer limitation and increased desorption of contaminants by continuous mixing (Christodoulatos and Koutsospyros 1998). Further, controlled environmental and nutritional factors such as pH, temperature and moisture, and bioavailabilty of nutrients and oxygen promote microbial growth and activity.

The Petrozyme Process The Petrozyme Process is a reactor-based microbial process for the treatment of petroleum oily sludges. The Petrozyme process uses advanced fermentation technology to degrade petroleum hydrocarbons in the sludge producing a nonhazardous effluent with very low levels of hydrocarbon.

The core technology of the Petrozyme process involves high rate biodegradation of the hydrocarbons in a bioreactor using a naturally selected and acclimated indigenous bacterial culture supplemented with a carefully designed blend of nutrients containing sources of nitrogen, phosphate, essential minerals and a surfactant. Reactor design and process operating conditions promote growth of a highly active microbial population, which rapidly converts the petroleum hydrocarbons primarily to carbon dioxide and water. Laboratory tests have shown that most of bacteria involved are known oil-degrading bacteria such as species of Pseudomonas, Acinetobacter, Rhodococcus and Alcaligenes etc. A simplified process flow diagram is exhibited in Figure 1. It is evident that the bioreactor is an integral part of a complete treatment process including recovery of recyclable oil, biodegradation of hazardous organic compounds, dewatering and disposal of treated sludges. The Petrozyme bioreactor system is modular can easily be scaled to accommodate the sludge treatment requirements. Any existing oil storage tanks or separators can be retrofitted and converted into bioreactors. Typical annual treatment capacities range from 2,000 to 15,000 m3. Alternatively, mobile tanks up to 75 m3 capacity can be equipped with required utilities to develop a bioreactor. A unit of this size is capable of processing 1200 2000 m3 of sludges annually. To operate the bioreactors, sludge and nutrient medium are mixed and inoculum is added to initiate the process. Depending on sludge type and composition, 50 to 80% of oily sludge is mixed with 20 to 50% nutrient medium

and inoculum on a volume basis. In most cases, the inoculum is developed on site using a unique method, which stimulates the indigenous bacterial population originating in the untreated oily sludge. The sludge oil is emulsified into a homogeneous suspension by the nutrient medium to make the oil available to the bacteria. The bioreactor conditions such as pH, temperature, aeration and nutrients have been optimized for the consistent performance. The degradation of TPHs is monitored over the treatment period. In the bioreactor, >90% of total petroleum hydrocarbons (TPH) as determined by hexane extractable material contained in the sludge are degraded. Typical sludge treatment time at 28-32C and pH 6.6-7.6 is 6-12 days depending on the composition of sludge and the required treatment standards. After successful treatment, 50-80% of the processed material is removed for disposal and the reactor is recharged with another batch of oily sludge and nutrients. In this manner, 20-50% of the volume that is left in the reactor serves as an inoculum for the subsequent run. Typical biodegradation profile in Petrozyme process at pilot tests (1-30 m3) and over one hundred batches in full-scale operations (60-130 m3) is exhibited in Figure 2. A consistent performance at various scales is evident from the curve. The TCLP analysis of the treated solids from refinery wastewater sludges from two different US refineries is shown in Table 2. Based on the US EPA criteria for treating listed hazardous wastes, these results indicate that the solids treated with Petrozyme process are treatable to non-hazardous levels. With some sludges, a small amount of oil separates to the surface at the end of the batch process which can be recovered sent to the refinery for

recycling. The aqueous residue containing low levels of TPHs can be sent to the wastewater system. The residual solids can be placed on a landfarm; de-watered and reused in asphalt or other industrial purposes; or disposed of cost- effectively to a non-hazardous landfill. Alternatively, where the sludges are stored in pits the treated non-hazardous residual solids can be placed back in the pit, covered with clean soil and returned to productive use.

CONCLUSION The results from pilot-scale testing and full-scale operations have demonstrated that Petrozymes bioreactor-based process is a technically advanced, regulatory compliant and cost-effective alternative for on-site oily waste treatment. The process is easy to use and sufficiently robust to accommodate oily sludges with varied composition. The toxic and mobile hydrocarbons are effectively degraded making treated sludge non-hazardous for a low-cost disposal.

References Atlas, R.M. and C.E. Cerniglia 1995. Bioremediation of petroleum pollutants: Diversity and environmental aspects of hydrocarbon biodegradation. BioScience, 45, 332-338. Boopathy, R. 2000. Factors limiting bioremediation technologies. Bioresource Technology, 74, 63-67. Christodoulatos, C. and A. Koutsospyros 1998. Bioslurry reactors. In: Eds. G.A. Lewandowski and L.J. DeFilippi, Biological treatment of hazardous waste, New York, John Wiley & Sons, 69-101. Devinny, J.S. and R.L. Islander 1989. Oxygen limitation in land treatment of concentrated waste. Hazardous Waste and Hazardous Materials, 6, 421-426. Huesemann, M.H. 1994. Guidelines for land-treating petroleum hydrocarboncontaminated soils. Journal of Soil Contamination, 3, 299-318. Manning, F.C. and R.E. Thompson 1995. Oilfield Processing, Voume 2. Crude Oil, Tulsa, PennWell Books, p. 5. Prince, R.C. 1993. Petroleum spill bioremediation in marine environments. Critical Reviews in Microbiology, 19, 217-242. Speight, J.G. 1991. The Chemistry and Technology of Petroleum. New York, Marcel Dekker Inc., p. 209. Ward, O.P. 1991. Bioprocessing. Milton Keynes, Open University Press, p. 160.

Legends to the figures

Figure 1. An integrated approach to the petroleum waste management Figure 2. Biodegradation profiles in Petrozyme process Results of pilot tests and full-scale operation.

Table 1. Composition of various petroleum oily sludges Oily sludge type Tank Clay bottoms fines 20-40 10-15 15-30 60-80 30-65 10-30

Composition TPH* (%) Solids (%) Water (%) Hydrocarbons (% of total) Saturates Aromatics Resins Asphaltenes
*

Refinery K&F 10-30 5-20 50-85

Refinery biosolids 2-5 2-10 80-90

Oil sands 10-20 50-70 10-30

Drilling mud 5-30 10-80 10-80

30-50 15-45 5-15 5-20

50-70 10-20 5-10 5-10

20-30 30-50 10-15 15-20

45-50 20-25 5-10 15-20

20-30 30-40 10-20 10-20

TPH = Total petroleum hydrocarbons determined as hexane extractable material

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Table 2. TCLP results after Petrozyme Process treated refinery sludge Component Benzene Toluene Ethylbenzene Xylenes Naphthalene Fluorene Anthracene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(a)pyrene Dibenzo(ah)anthracene Phenol 2,4-dimethyl phenol o,m,p- Cresol Nitrobenzene Benzyl butyl phthalate Bis-ethylhexyl phthalate Dioctyl phthalate
*

*MALs (mg/L) 0.135 0.08 0.057 .032 0.059 0.059 0.28 0.068 0.067 0.059 0.059 0.11 0.061 0.055 6.2 18.9 54 0.0969 9.29 0.28 0.017

TCLP Refinery 1 (mg/L) <0.050 <0.050 <0.050 <0.050 0.0016 <0.001 <0.001 <0.001 0.0009 <0.001 <0.001 <0.001 <0.001 <0.001 0.0041 <0.0025 <0.0025 <0.0025 <0.0025 0.023 <0.010

TCLP Refinery 2 (mg/L) <0.0025 <0.005 <0.005 <0.005 <0.001 <0.001 <0.001 <0.001 0.0021 <0.001 <0.001 <0.001 0.00022 <0.00005 0.0015 <0.0025 <0.0025 <0.0025 <0.0025 <0.01 <0.01

For delisting of wastes, the U.S. EPA typically evaluates a petitioned wastes leachate data as determined by an appropriate leaching test, using an appropriate fate and transport model. The leaching test used is the Toxicity Characteristic Leaching Procedure (TCLP).

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Figure 1.

E & P OILY WASTE Pit sludges, drilling muds, contaminated soil, clay fines

REFINERY OILY WASTE API and DAF sludges, tank bottoms, biosolids

Recovered oil to Slop oil tank OIL RECOVERY (Optional) Oily water to bioreactor

Oily solids/clay fines to bioreactor

PETROZYME BIOREACTOR

Inoculum Nutrients

Air Treated material

Non-hazardous landfill

Back to cleaned pit & capped

Landspreading

Reuse Asphalt paving

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Figure 2.

120

100 % of initial TPH remaining

Full-scale runs

80
Pilot tests demo

60

40

20

0 0 3 6 Tim e (da ys) 9 12

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