Iranian Journal of Science & Technology, Transaction B, Engineering, Vol. 30, No.

B5
Printed in The Islamic Republic of Iran, 2006
Shiraz University

TREATMENT OF OIL-CONTAMINATED DRILL CUTTINGS

OF SOUTH PARS GAS FIELD IN IRAN USING
*
SUPERCRITICAL CARBON DIOXIDE
I. GOODARZNIA1 AND F. ESMAEILZADEH2**
1

Dept. of Petroleum and Chemical Engineering, Sharif University of Technology, Tehran, I. R. of Iran
2
Dept. of Petroleum and Chemical Engineering, Shiraz University, Shiraz, I. R. of Iran
Email:esmaeil@shirazu.ac.ir
Abstract New treatment technologies are currently being investigated for the treatment of
contaminated drilling waste mud with oil. Supercritical fluid extraction is a promising technology
that could be effectively used to extract this contaminated drilling waste mud. In this work, one
step extraction efficiency of supercritical carbon dioxide to drilling waste mud of South Pars gas
field has been investigated at a range of temperatures (55 to 79.5 C), and over a pressure range of
160 to 220 bar. Extraction efficiencies were calculated based on cuttings weight loss. Results show
that approximately 28.45 % of cuttings weight loss in one step extraction at a pressure of 200 bar
and temperature of 60 C can be extracted by supercritical carbon dioxide.

Keywords Supercritical carbon dioxide, contaminated drilling waste mud, experimental apparatus

1. INTRODUCTION
Supercritical fluid extraction is a new separation technique which has drawn much attention to the use of
supercritical fluids as extraction solvents in separation processes [1-4]. Carbon dioxide is a promising
solvent since it is inexpensive, non toxic, non-inflammable, environmentally acceptable and has a low
critical temperature and a moderate critical pressure.
The drilling of wells for the recovery of valuable materials such as petroleum is relatively expensive,
both to the equipment employed in the drilling procedures and in the corollary activities to insure that the
environment of the area surrounding the well is not injured. Drilling for oil and gas wells involves the use
of drilling mud. Drilling muds are fluids used to control formation pressures, lubricate and cool the bit,
remove rock fragments from the drilling well, and form a consolidated wall cake on the sides of the hole
prior to casing. These muds, which are highly viscous, are complex formulations and include such finely
divided materials as ground ilmenite, bentonite, various clays, barite, lead ore, fibers, hulls, etc. in a liquid
medium which may be aqueous (e.g., water or brine) or an oil (e.g., diesel oil). In the drilling of wells for
the production of petroleum, large amounts of drilling cuttings are produced and carried by the circulating
mud that passes through the drilling equipment and is then returned to the earths surface. At the earths
surface, the drill cuttings are separated from the drilling mud through the use of various mechanical solids
control equipment such as screens, shakers, solid separators, desanders, mud cleaners, desilters and the
like.
The drill cuttings are composed of the drilling mud and solid particles. In general, three types of muds
are currently in use: oil-based muds, water-based muds and synthetic-based muds. Oil base muds are
composed primarily of diesel oil or mineral oil and additives. Water-based oil consists of a base of salt

Received by the editors January 15, 2006; final revised form September 18, 2006.
Corresponding author

608

I. Goodarznia / F. Esmaeilzadeh

water or fresh water containing additives, while synthetic-based muds have oil-like base materials. Waterbase muds are not able to perform as well as oil-base muds in deep wells with high temperature
conditions. Synthetic-based muds generally perform better than water based muds, but less than oil base
muds. Oil-based muds are well suited for high temperature conditions because oil-base muds are
paraffinic in nature with a relatively high boiling range. In addition, it is a common practice to employ an
oil based drilling fluid. The drill cuttings produced by an oil based drilling fluid are rather heavily
contaminated by the oil base which is used for preparing the drilling fluid. These drilling waste/cuttings
must be treated. In other words, the oily drill cuttings can not be discharged directly into a disposal site at
the well, not only because of their adverse effect upon the environment, but additionally because the great
value of the oil contained in them. It has been a common practice to treat the oil drill cuttings in order to
produce a solid material that can be disposed into the environment surrounding the well site without injury
to it. Various approaches have been attempted to remove the oil from the rock [5-6]: such as the use of a
high temperature [7], liquid solvent extraction [8] and soap and water washing [9]. The chemical wash
system is also described in references [10-11]. In this system, the oily drill cuttings are treated with
various chemicals including detergents with relatively intense mixing. Then, this mixture is resolved into
relatively oil-free solids (i.e., the drill cuttings) and a recovered liquid phase which is a mixture of water,
oil and the detergents which were employed in the chemical wash system. The solids could be disposed of
by burial or other means, however, they may contain sufficient oil that upon contact with bodies of water,
such as surface waters, lakes or the ocean, a rainbow effect will be produced, which is unacceptable
relative to preserving the environment in the best possible form. In addition, the liquid phase must be
treated to separate the oil from the bulk water phase so that the water portion can be discharged or
otherwise disposed of without pollution problems. The separated oil can be utilized for various uses such
as fuel or be returned into the blending of additional oil based drilling muds and the like. One objection to
the chemical wash system is it's relatively high cost in the amount of above several hundred dollars a day,
merely from the chemical requirements. Various thermal systems for driving the oily phase from the solids
of the drill cuttings through the use of thermal energy have been proposed. The greatest disadvantage in
this particular procedure for treating oily drill cuttings is the danger of explosions in the system if air or
other oxidizing gas enter into contact with the heated oil vapors produced by the excessive heating of the
oily drill cuttings. Should the flow of inert gas be terminated through accident or inadvertence, air entering
into contact with these oily vapors could produce a very serious explosion and fire. Such an arrangement
is not acceptable in the area surrounding an oil well, especially while it is being drilled. Bioremediation
enables the oil in the drilling waste to be biologically degraded using hydrocarbon-degrading
microorganisms. One major drawback of bioremediation is the extensive time required for satisfactory
remediation. Drilling waste can also be re-injected into underground oil-bearing formations, away from
the groundwater. However, if re-injection of the waste is not technically or economically feasible, the
waste must be treated to reduce oil concentration prior to final disposal. There is also the risk of
groundwater contamination during re-injection.
All these techniques suffer from safety, complexity or high-energy use problems. To overcome the
limitations of current drilling waste treatment and disposal options, alternative technologies are being
investigated for the treatment of oil-contaminated drill cuttings. Supercritical fluid technology is a
favorable method for treatment of oil-contaminated drill cuttings. Supercritical fluids have several
desirable properties that make them attractive for certain separation processes, e.g. the product is not
contaminated with residual solvent [2-3]. The SFE processes used are environmentally-friendly, inert,
cheap and are widely-available. Supercritical carbon dioxide exhibits excellent solvating characteristics
which are easily manipulated to dissolve non-polar compounds like diesel and mineral oils. Treatment of
drill cuttings using supercritical carbon dioxide would also provide the added benefit of allowing recovery
and reuse of the expensive oil-based muds. In addition, treatment by supercritical carbon dioxide can be
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Treatment of oil-contaminated drill cuttings of

609

performed on-site in extraction vessels, thus eliminating the need for extensive land treatment. In the case
of offshore operations, supercritical fluid extraction of oil-contaminated drill cuttings would eliminate
expensive transportation of offshore-generated cuttings to shore for treatment and disposal.
In this work, the extraction of oil in drill cuttings by supercritical carbon dioxide was carried out at a
pressure range of 160 to 220 bar and over a temperature range of 55 to 79.5 C by a flow type apparatus.
2. EXPERIMENTAL SECTION
a) Materials
The carbon dioxide supplied by Roham Gas Chemical Co., Iran, had a minimum purity of 99.8 mol %.
The oil-contaminated drill cuttings were donated by National Iranian Oil Company (N.I.O.C-Pars Oil Gas
Company).
b) Procedure
A flowtype apparatus as shown in Fig. 1 was used to extract the oil from waste drilling mud cuttings
by supercritical carbon dioxide. A detailed description of the equipment and operating procedures was
reported previously [8]. Cuttings weight loss was determined from the weight of extracted solutes and the
weight of cuttings charge. The liquefied carbon dioxide was pressurized using a high-pressure air driven
oil-free reciprocating pump. Pressurized carbon dioxide flowed into a surge vessel to dampen the
fluctuations generated by the operation of the pump, a heating coil and finally to the extraction vessel. The
preheater and extraction vessel were immersed in a constant-temperature water-circulating bath. The
temperature inside the water bath was regulated within 0.3 K through the use of a heating element and a
proportional type temperature controller using a PTC thermocouple. The vessel outlet was packed with
glass wool to prevent particle entrainment. The carbon dioxide leaving the extraction vessel was then
depressurized through a heated needle valve. The depressurized carbon dioxide then passed through a cold
trap which was submerged in an ice bath. The system pressure was measured by a Bourdon gauge with a
division of 2 bar in the range of 0-250 bar. The system pressure was constant to within 1 % of the
desired value throughout the experiment. Typically, the amount of solutes collected was in the order of
1.3-2.7 g. The extraction process involved a 1 hour and 30-minute cycle: one hour static extraction (no
flow of SC CO2 through the vessel) followed by a 30-minute dynamic extraction. Solvent flow rates used
in this study for oil contaminated drill cuttings range from 0.124 to 0.398 standard m3/h. Within this range,
the flow rate has a negligible effect on the experimental results. The reliability of the apparatus was
preliminarily tested by measuring the solubility of naphthalene in supercritical carbon dioxide at 35 0 C
over a pressure range of 98-200 bar as reported in reference [12].

Fig. 1. Schematic diagram of experimental apparatus

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I. Goodarznia / F. Esmaeilzadeh

610

3. RESULTS AND DISCUSSION

Extractions of raw drill cuttings of South Pars gas field in Iran were carried out at various conditions of
temperature and pressures as shown in Table 1.
Table 1. Experimental test conditions for supercritical fluid of carbon dioxide
Sample no.
1
2
3
4
5
6
7
8
9

Extraction conditions
(bar, C)
160 bar, 60 C
180 bar, 60 C
200 bar, 55 C
200 bar, 60 C
200 bar, 60 C
200 bar, 60 C
200 bar, 60 C
200 bar, 79.5 C
220 bar, 60 C

Cuttings
charge (g)
5.8
5.8
4.2
5.7
5.4
5.2
5.1
5.5
5.8

CO2 flow rate at

Weight of
Cuttings weight standard conditions
extracted oil (g)
loss (%)
(ft3 min-1)
0
0
0.0702
1.3
22.4
0.0727
1.1
26.2
0.2456
1.7
29.8
0.1686
1.6
29.6
0.2065
1.4
26.9
0.2341
1.4
27.5
0.1736
2.7
49.1
0.1187
1.8
31.0
0.0812

The data seem to indicate that the cutting weight loss may increase with increasing temperature and
pressure. The extraction efficiency is more sensible by changing temperature rather than pressure. The
experimental results also show that, the supercritical carbon dioxide cannot extract oil below the pressure
range of 160 bar. For a pressure of 200 bar and a temperature of 60 C, the average extraction efficiency is
28.45 %.
The weight minute space velocity (WMSV) is defined as the mass flow rate of the solvent divided by
the mass of cuttings and oil initially in the extractor. The weight minute space velocity (WMSV) at 200
bar pressure and 60 C for extraction of oil in waste drilling mud by supercritical fluid of carbon dioxide
versus residence time is given in Table 2 and Fig. 2.
Table 2. Experimental data of weight minute space velocity (WMSV) versus
residence time at 200 bar and 60 C
Sample no.
4
5
6
7

WMSV (min-1)
1.66
2.146
2.527
1.9105

Residence time (min)

36
27
22
29.4

Cuttings Weight loss (%)

30
29.5
29
28.5
28
27.5
27
26.5
55

56

57

58

59

60

WMSV Residence Time

WMSV.Residence
Time

Fig. 2. Carbon dioxide extraction results at 200 bar pressure and 60 C

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Results show that the (WMSV Residence time) values greater than 58, similar to hydrocarbon removal
were obtained.
Visual observations were made before and after extraction. The raw cuttings prior to extraction by
supercritical carbon dioxide appeared extremely viscous and dark in color. Once the extraction was
completed, the color of cuttings changed to light gray and the extracted oil appeared yellow in color.
4. CONCLUSION
The experimental data of oil extraction from waste drill cuttings have been presented in supercritical
carbon dioxide at a pressure and temperature range of 160 to 200 bar and 55 to 79.5 oC respectively. A
minimal extraction efficiency of 22.4 % was obtained with extractions at 180 bar and 60 oC. The
experimental results show that at a high constant pressure, the extraction efficiency is increased by
increasing temperature. Also, for each condition of extraction with supercritical fluid, there is an optimum
value of (WMSV residence time) to extract the oil from waste drilling mud.
Acknowledgement- The authors are grateful to the Sharif and Shiraz Universities for supporting this
research. This study was part of a research project sponsored by the R & D N.I.O.C-Pars Oil Gas
Company, which is gratefully acknowledged.
REFERENCES
1.

Brennecke, J. F. & Eckert, C. A. (1989). Phase equilibria for supercritical fluid process design. AICHE J., 35,
1409-1427.

2.

Esmaeilzadeh, F. & Goodarznia, I. (2005). Supercritical extraction of phenanthrene in the crossover region. J.
Chem. Eng. Data, 50, 49-51.

3.

Esmaeilzadeh, F. & Goodarznia, I. (2005). Separation of phenanthrene from anthracene oil using supercritical
carbon dioxide. Chem. Eng. Technology, 28, 106-109.

4.

McHugh, M. A. & Krukonis, V. J. (1986). Supercritical fluid extraction principles and practice. Butterworths:
Boston, MA.

5.

William, A. T. (1972). Apparatus for treating drill cuttings at offshore locations. U. S. Patent 3688781.

6.

Risher, O. T., Fitch, N. J., Billeaud, M. D., Tilley, D. J., & Landry, R. C. (2006). Method and apparatus for
removing fluids from drill cuttings. U. S. Patent 7093678.

7.

Heihecker, J. K. & Schoeneman, D. D. (1982). Dryer system for drilling mud cuttings. U. S. Patent 4319410.

8.

Heihecker, J. K., Williams, R. E. & Marshal, W. H. (1989). Apparatus and method for removing and recovering
oil and/or other oil based drilling mud additives from drill cuttings. International Patent 89/02774.

9.

George, J. M. & Smith, J. D. (1984). Method and apparatus for washing drilling cuttings. U. S. Patent 4462416.

10. Heilhecker, J. K. & Robinson, L. H. (1973). Method and apparatus for treating a drilling fluid. U. S. Patent
3766997.
11. Teague, L. P. (1975). Apparatus for avoiding water pollution at an offshore drilling site. U. S. Patent 3860019.
12. Goodarznia, I. & Esmaeilzadeh, F. (2002). Solubility of an anthracene, phenanthrene, and carbazole mixture in
supercritical carbon dioxide. J. Chem. Eng. Data, 47, 333-338.

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