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Treatment and Recovery of Oil-Based Sludge Using Solvent Extraction

Article · November 2008

DOI: 10.2118/118179-MS

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SPE 118179

Treatment and Recovery of Oil-Based Sludge Using Solvent Extraction

Dana M. Abouelnasr and Essam Zubaidy, American University of Sharjah
Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 Abu Dhabi International Petroleum Exhibition and Conference held in Abu Dhabi, UAE, 3–6 November 2008.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract

Oil-based sludge is a common by-product of petroleum processing, storage, and transport. It is currently treated to a
minor extent before it is disposed of in a landfill. However, as energy costs rise, and environmental impacts become of greater
concern, there is increased interest in developing a means to reduce the amount and toxicity of this waste, and to recover useful
materials.
Solvent extraction was used to treat oil-based sludge from oil tankers. Methyl ethyl ketone (MEK) and LPG
condensate were among the solvents used. Different solvent-to-waste ratios by weight were used to determine the optimum
process. The mixture was then filtered, and solvent was recovered from the filtrate through distillation. The extraction and
filtration steps were at ambient temperature. The recovered fuel oil was analyzed for fuel charactistics.
The maximum recovery of fuel oil occurred with a four-to-one ratio of MEK to sludge. Thirty-nine percent of the
sludge mass was recovered as fuel oil using this system. On analysis, the recovered fuel oil was similar to typical fuel oils,
except for elevated levels of carbon residue and sulfur.
This solvent extraction process can be implemented as a continuous process to reduce the amounts of waste oil-based
sludge, while recovering valuable fuel oil.

Introduction

Petroleum refining industries generate relatively large amounts of waste from various sources including waste water,
tank bottoms, slop oil emulsion solids and various sludges from oil/water/solids separation. The accumulation of crude storage
tank bottoms is a comparatively serious problem experienced by most refineries worldwide. The settling out of sand, rust and
heavy fractions of crude oil results in a loss of ullage in the refinery crude storage tanks and can ultimately cause refinery
problems when sludge is introduced into the plant. It can cause below-optimal crude throughputs and fouling of heat
exchangers. And when solids or emulsions pass from one area to another, an increase in production down-time can result.
Since sludge has previously been disposed of at landfill sites and lagoons, valuable hydrocarbons have been lost, which has
both environmental and financial implications. As this method of disposal becomes widely unacceptable, alternative solutions
providing oil recovery, re-use and recycling are essential.
Petroleum refinery sludges typically comprise three phases and multiple components. They usually contain 20-90
wt% water, 5-40 wt% oil and about 5-35 wt% solids. Several studies have been reported in which processes have been used to
deal with petroleum-based sludge, usually by separating it into its different phases. Elektorowicz et al. (2006) showed that
oily sludge is a water-in-oil emulsion, stabilized by fine solids. They investigated the effect of different electrical potential
gradients and amphoteric surfactant on phase coalescence and separation. Several other studies detail processes which have
been used to deal with petroleum-based sludge. Jean and Lee (1999) used high-pressure filtration to recover hydrocarbon
liquor from petroleum-based sludge. The slow mechanical expression of the lighter hydrocarbons proved to be inefficient,
although cationic polyelectrolyte conditioning slightly enhanced the de-liquoring rate, and a freeze/thaw treatment
significantly improved the process, Jean et al. (1999). The treated sludge comprised three distinct layers, an oil layer on top, a
sediment layer at the bottom and an aqueous layer in between. This method was able to separate over 50% of the oil content in
the sludge. Lane (1991) demonstrated a process for treating petroleum refinery sludge using steam to produce lighter
hydrocarbon product and a solid coke residue. Couillard et al. (1991) cleaned beach sand which had been contaminated by an
petroleum-based sludge and an accidental oil spill. They used pressurized hot water, which recovered most of the oil, and
produced solids (mostly beach sand) containing only traces of oil Biceroglu (1994) demonstrated a process for removing oil
from oily wastes using extraction. The process uses a refinery hydrocarbon stream as the extractive solvent. Waste solids are
2 SPE 118179

either used for fuel, or disposed of in a landfill. Kam (2001) used three different treatment processes for petroleum-based
sludge: sonication, extraction, and thermal desorption. All three processes recovered similar amounts of lighter hydrocarbon.
Sanders and Veenstra ( 2001) observed that, although petroleum-based sludge does not contain significant amounts of
hazardous substances, it is not acceptable as a road-base material. Ramaswamy, et al. (2006) introduced the air flotation
method to recover oil from synthetically-prepared oily sludge. Commercial surfactant was used as a collector and frother using
various parameters such as flotation time, initial amount of oil in the feed, and the amount of surfactant required for oil
recovery. The maximum oil recovery obtained was 55%. Trowbridge and Holcombe (1995) used dehydration and solvent
extraction on petroleum-based sludge. The process produced clean, dry solids suitable for disposal in a non-hazardous landfill,
water which is treatable in an industrial waste water treatment plant, and indigenous oil which may by recycled or disposed of
at less cost because its volume is smaller than the original waste feed. Shie, et al. (2003) converted oil sludge into useful
resources such as lower molecule-weight organic compounds and carbonaceous residues by pyrolysis with nitrogen as a carrier
gas. They investigated the influences of using sodium and potassium compounds as additives on improvement of pyrolysis
process of oil sludge.
In this work, recoverable oil was extracted from petroleum-based sludge using several different solvents. The
characteristics of the recovered oil are then compared to that of commercially-available fuel oil, to determine whether it is
acceptable as a fuel.

Materials and Methods

Oily sludge was obtained from a local environmental service company in the UAE. The sludge had been physically treated by
the company to remove most of the water and solid material. This material is the feedstock for this work. Methyl ethyl ketone
(MEK), heptane, hexane, iso-propanol, and iso-butanol solvents were obtained from a local vendor. LPG condensate was
provided by a local facility. Its major components are shown in Table 1.

The main steps of the process are:

1. The oil sludge was added to a specific amount of each solvent. Weight ratios of solvent-to-sludge varied between 1:1
and 6:1 MEK and LPG Condensate.
2. The mixture was stirred for 2 hours using an overhead stirrer at room temperature.
3. The mixture was settled and filtered; the filtrate was comprised of the recovered oil and the solvent.
4. The filtrate was subjected to simple distillation for solvent recovery.
5. The optimal solvent-to-sludge ratio was determined based upon oil recovery. This ratio was then used with other
solvents: heptane, hexane, iso-propanol, and iso-butanol.
6. The recovered oil was analyzed quantitatively as well as qualitatively, and physical properties such as specific
gravity, flash point, viscosity, Conradson carbon residue, ash content, asphaltene content as heptane-insolubles, water
content, sulfur content, and heat of combustion were measured according to ASTM Standards.

Results and Discussion

For two solvents, several solvent-to-sludge ratios were used in the extraction step. For each ratio, the mass of the
recovered oil was measured. The oil recovery as a weight percent of the original sludge increases almost linearly with
increasing ratio, for both MEK and LPG condensate. The percentage of oil recovery reaches a maximum for both MEK and
LPG condensate at a solvent-to-sludge ratio of 4:1, and then remains relatively constant with increasing ratio. The maximum
oil recovery for MEK was 39%, and for LPG condensate was 32%. Physical properties were measured for the recovered oil
for all solvent-to-sludge ratios. These physical properties include carbon residue, ash content, and asphaltene content as
heptane insolubles. These properties are shown in Figure 1 for MEK and Figure 2 for LPG condensate. Ash content decreases
rapidly with increasing solvent ratio, and quickly reaches a minimum at a ratio of 2:1 or 3:1. Carbon residue and asphaltene
content both show a decrease with increasing ratio, with a minimum at 4:1. From this information, 4:1 was chosen as the
optimal solvent-to-sludge ratio.
This ratio was then used with the other solvents, hexane, heptane, iso-propanol, and iso-butanol. The percentage of
oil recovery for all solvents at this ratio is plotted in Figure 3. The oil recovery for MEK was the highest. The next-highest
percent oil recovery was for LPG condensate. The percent oil recovery then decreased with decreasing molecular weight:

MEK > LPG Condensate > Heptane > Hexane > iso-Propanol > iso-Butanol

Alcohols provided the poorest performance, with iso-butanol providing the minimum oil recovery of 8%.
The Conradson carbon residue, ash content, and asphaltene content as heptane insoluble of the recovered oil with
different solvents are shown in Figures 4 through 6, respectively. MEK consistently produces the lowest, or among the lowest
content of carbon residue, ash, and asphaltene. The properties for recovered oil using 4:1 MEK are listed in Table 2.
SPE 118179 3

This recovered oil is similar to commercially-available heavy fuel oil, although the carbon residue and sulfur content
are higher than is desirable for fuels. The high sulfur content is related to the original sulfur content in the petroleum which
produced the oil sludge. The sulfur content must be reduced before this oil can be used as fuel to reduce corrosion and
environmental pollution.
To study the effect of temperature, one extraction was carried out at an elevated temperature, 50o C, using LPG
condensate as the solvent, and a solvent-to-sludge ratio of 4:1. The physical properties and the amount of oil extracted are
shown in Table 3. Comparing these values to those using LPG condensate at room temperature, the amount of recovered oil
has increased from 32% to 38.5%, a 20% increase. The physical properties were also changed; exhibiting higher carbon
residue, ash content, and asphaltene content compared with extraction at room temperature.

Conclusion

The large quantity of oil sludge requires consideration regarding the optimum treatment to recover valuable
hydrocarbons. The work described in this paper demonstrated a recovery of 39 wt % of the total amount of sludge using MEK.
The physical properties of the recovered oil indicate that it could be used as a fuel oil after some treatment to reduce the sulfur
content to acceptable levels.

References

Biceroglu, O., 1994. Rendering oily waste land treatable or usable. US Patent 5,288,391.

Couillard, D., Tran F.T., Tyagi, R.D., 1991. Process for the in situ restoration of oil-contaminated soils. Journal of
Environmental Management, 32, 19-34.

Elektorowicz, M., Habibi, S., Chifrina, R., 2006. Effect of electrical potential on the electro-demulsification oil oily sludge.
Journal of Colloid and Interface Science. 295, 535-541.

Jean, D.S., Lee, D.J., 1999. Expression deliquoring of oily sludge from a petroleum refinery plant. Waste management, 19,
349-354.

Jean, D.S., Lee, D.J., Wu, J.C.S, 1999. Separation of oil from oily sludge by freezing and thawing. Water Research , 33, 1756-
1759.

Kam, E.K.T., 2001. Assessment of sludge and tank bottoms treatment processes. Proc of the 8th International Petroleum
Environmental Conference. Houston.

Lane, G.M., 1991. Process for treating oil sludge. US Patent 4,985,131.

Ramaswamy, B., Kar, D.D., De, S., 2006. A study on recovery of oil from sludge containing oil using froth flotation. Journal
of Environmental Management, 85, 150-154.

Sanders, D.A., Veenstra, J.N., 2001. Pollution prevention and reuse alternatives for crude oil tank bottom sludges, Proc of
the 8th International Petroleum Environmental Conference. Houston.

Shie, J., Lin, J., Chang, C., Lee, D., Wu, C., (2003). Pyrolysis of oil sludge with additives of sodium and potassium
compounds. Journal of Resources, Conservation and Recycling, 39, 51-64.

Trowbridge, T.D., Holcombe, T.C., 1995. Refinery sludge treatment/hazardous waste minimization via dehydration and
solvent extraction. Journal of the Air and Waste Management Association,
4 SPE 118179

Tables

Table 1: Major components of the LPG Condensate (information provided by the facility supplying the product)

Nitrogen 0.00 wt% iso-Pentane 2.573 wt%

Carbon dioxide 0.569 wt% n-Pentane 2.654 wt%
Methane 3.169 wt% Hexanes 5.503 wt%
Ethane 3.082 wt% Heptanes 10.933 wt%
Propane 5.168 wt% Octanes 15.433 wt%
Iso-Butane 2.269 wt% Nonanes 12.148 wt%
n-Butane 4.286 wt% Decanes 9.092 wt%

Table 2: Properties of recovered oil using 4:1 MEK as the solvent

Property Value
Specific gravity@15oC 0.8894
Flash point > 32o C
Viscosity@40oC 118.453 cst
Carbon residue 2.136 wt%
Ash content 0.0819 wt%
Asphaltene content as heptane
0.524 wt%
insolubles
Water content Nil
Sulfur content 2.72 wt%
Heat of combustion 44996 J/g

Table 3: Properties of recovered oil using 4:1 LPG condensate as the solvent at 50o C

Property Value
Oil recovery 38.5 wt%
Specific gravity 0.899
Carbon residue 5.110 wt%
Ash content 0.099 wt%
Asphaltene content 0.723 wt%
SPE 118179 5

Figures

Figure 1: Physical properties of the recovered oil as a function of solvent-to-sludge ratio

using MEK as the solvent

Figure 2: Physical properties of the recovered oil as a function of solvent-to-sludge ratio

using LPG condensate as the solvent
6 SPE 118179

Figure 3: Percent oil recovery for all solvents, using a solvent-to-sludge weight ratio of 4:1

Figure 4: Carbon residue in recovered oil for all solvents,

using a solvent-to-sludge weight ratio of 4:1
SPE 118179 7

Figure 5: Ash content in recovered oil for all solvents,

using a solvent-to-sludge weight ratio of 4:1

Figure 6: Asphaltene content as heptanes-insolubles in recovered oil for all solvents,

using a solvent-to-sludge weight ratio of 4:1.01

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