Fuel 118 (2014) 214–219

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Characterization of emulsified water in petroleum sludge

Qunxing Huang ⇑, Feiyan Mao, Xu Han, Jianhua Yan, Yong Chi
State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China

h i g h l i g h t s

 DSC analysis was employed to characterize emulsified water and salt in petroleum sludge for the first time.
 A new mathematic equation was proposed for obtaining the size distribution of water droplets in petroleum sludge.
 Three different kinds of petroleum sludge have been studied to predict proper treatment method.

a r t i c l e i n f o a b s t r a c t

Article history: Increasing depletion of conventional oil resources has driven interest in recovery of oil resources from
Received 4 August 2013 petroleum sludge. To improve the quality of recovered oil, it is essential to maximize the removal of
Received in revised form 4 October 2013 emulsified water, dissolved salts, and other impurities. Therefore, this study was conducted to character-
Accepted 23 October 2013
ize the emulsified water droplets and salt in petroleum sludge through differential scanning calorimetry
Available online 9 November 2013
(DSC). To accomplish this, samples of three different types were evaluated before and after centrifuga-
tion. The results indicated that with DSC water content and eutectic of salt hydrates could be identified
Keywords:
during controlled heating from 60 °C to room temperature. Moreover, a new equation to retrieve water
Petroleum sludge
Differential scanning calorimetry
droplets size distribution according to the cooling phase of the DSC thermogram from 50 °C to 60 °C is
Water-in-oil emulsion proposed. Samples collected from a mixed petroleum sludge storage tank and a tank cleaning wastewater
Size distribution reservoir were found to contain emulsified water droplets with a broadened size distribution, and the
freezing peaks shifted from 44 °C to 20 °C as the diameter of water droplets increased. Additionally,
water droplets in the sample collected from the crude oil storage tank were very strongly emulsified
and were relatively uniform, with a diameter of 2.7–3.3 lm. Following centrifugation, small droplets
were found in the upper oily layer, suggesting that de-emulsification pre-treatment prior to water/oil/
solid phase separation is essential to obtain high-purity oil resources. This is the first time DSC is
employed to characterize emulsified water and deduce water droplets size distribution in petroleum
sludge. These results are essential and useful for optimization of petroleum sludge treatment.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Petroleum sludge is a major waste generated during crude oil
production, transportation, storage, and refining. Petroleum sludge
can generally be considered a complex emulsion of aqueous drop-
lets dispersed in petroleum liquid that typically contains 30–80%
oil, 30–50% water, and 10–20% solids by mass. Petroleum sludge
is known as a potential energy material and can be used as a fuel
for cement kilns, crude distiller feedstock, and coking feedstock.
However, petroleum sludge contains many toxic species including
benzene, toluene, ethyl-benzene, xylene, polycyclic aromatic
hydrocarbons, and heavy metals. Thus, it is classified as hazardous
⇑ Corresponding author. Address: Institute for Thermal Power Engineering, Zheda
Road No. 38, Zhejiang University, Hangzhou 310027, China. Tel.: +86 571
87952834; fax: +86 571 87952438.
E-mail address: hqx@zju.edu.cn (Q. Huang).
waste in many countries [1] and inappropriate treatment may lead
to contamination of soil, groundwater, and the environment [2,3]
and pose threats to the health of local residents. As the second larg-
est consumer of crude oil in the world, more than 1,000,000 t of
petroleum sludge are generated in China annually. Therefore, it is
of great interest to recover oil from this waste to achieve economic
and environmental benefits. In the past several years, many tech-
nologies have been developed to recover hydrocarbons from petro-
leum sludge before final disposal [1,4]. These technologies are
based on individual or combinations of the following procedures:
(1) mechanical methods (e.g., centrifugation) [1,5]; (2) chemical
methods (e.g., solvent extraction) [6,7]; (3) biological methods
(e.g., microbial remediation) [8,9].
For petroleum sludge, water and salt are the most unwanted
components when the recovered hydrocarbons are used as chem-
ical materials or fuel. High water content will cause explosions
when the sludge is subjected to a burner or pressurized chemical

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.10.053
 Q. Huang et al. / Fuel 118 (2014) 214–219
reactor. Additionally, salt components, especially chloride, will
cause serious corrosion of industrial facilities and may deactivate
oil refinery catalysts. Therefore, the properties of water droplets
and salt are extremely important to the choice of sludge treatment
solution and improvement of the quality of recovered hydrocarbon
resources. Currently, methods of analyzing water content in petro-
leum sludge include proximate analysis [10,11], the Karl Fischer
reagent method [12], and the chemical distillation [7]. Salt content
can be measured through the ASTM method D3230 [7]. However,
the understanding of water droplets and salt components con-
tained in this complex multiphase waste is very limited. Most pre-
vious studies concerned with de-emulsification and desalting of
petroleum sludge have lacked effective characterization methods
because of its high viscosity and opacity and the coexistence of fine
solid particles with water droplets.
Thermal techniques are widely used as reliable and powerful
analytical tools for characterization of degradation, evaporation,
oxidation, and combustion of petroleum products and their deriv-
atives [13–16]. Differential scanning calorimetry (DSC) is a very
suitable technique for investigating the behavior of emulsions sub-
mitted to environments with changing temperatures. Clausse et al.
[17–20] and Avendano-Gomez et al. [21] have deduced the quanti-
tative properties of water-in-oil (W/O) emulsions, including water
droplets size distribution and heat flux during freezing and melt-
ing, and their research has indicated that DSC is a promising tool
for characterization of emulsions.
This study was conducted to investigate the characteristics of
W/O emulsions in petroleum sludge and to estimate the water
droplets size distribution after centrifugation treatment. To accom-
plish this, three different types of petroleum sludge were evaluated
before and after centrifugation through DSC and the results were
compared with those of chemically extracted samples. This is the
first time DSC is employed to characterize solidification and melt-
ing features of emulsified water droplets and eutectic of salt water
in petroleum sludge. A fitting equation was also proposed to de-
duce the water droplets size distribution from the heat release pro-
file. The results of this study will be useful for determining proper
petroleum sludge treatment methods to recovery energy resources
while alleviating environmental burdens.
2. Materials and methods
2.1. Materials
Three different petroleum sludge samples were evaluated. ZS
(Zhoushan Sludge) was collected directly from the bottom of a
crude oil storage tank in the port of Zhoushan. NS (Nahai Sludge)
was obtained from the bottom of tanks containing used oil tank
cleaning water at Nahai Solid Waste Central Disposal Co., Ltd. Dur-
ing collection of the sludge, oily water in the upper layer of the
same reservoir was also sampled. YS (Yimin Sludge) was collected
from a sludge tank storing mixed oily sludge with a complex com-
position in the Zhoushan Yimin Waste Recovery Plant.
All samples were subjected to a series of analyses to determine
their primary components. Water content in petroleum sludge was
determined by the ASTM-D95-05 procedure and total hydrocarbon
content was evaluated by soxhlet extraction using toluene as sol-
vent. SARA (saturates, aromatics, resins, asphaltenes) were first
separated by precipitation of asphaltene with n-hexane and mal-
tene, followed by further separation through a chromatographic
column according to ASTM-D2007-02. Analytical grade chemical
reagents were purchased from Sinopharm Chemical Reagent
Shanghai Co., Ltd.
215
2.2. Sample preparation prior to DSC analysis
For comparison, the samples of oil recovered from sludge
through Soxhlet extraction and centrifugation were also analyzed.
During Soxhlet extraction, 5 g of each sludge sample were washed
with 200 mL of toluene for 6 h, after which the weight of extracted
oil was measured gravimetrically following removal of the extract-
ing solvent through evaporation at 65 °C. For centrifuged sludge,
10 g of each sample were placed in a 120-mL centrifugal tube
and centrifuged at 2500 rpm/min, using a Thermo Scientific ST40
centrifuge for 20 min, after which the upper oil layer was collected.
For analysis, a 1.0-mL syringe was used to collect samples of the
petroleum sludge and recovered oil after mixing well, and one
droplet of the sample was gently deposited on a clean aluminum
crucible.
2.3. DSC analysis
The original petroleum sludge and the oil phase recovered from
Soxhlet extraction and centrifugation were submitted to a regular
heating and cooling cycle within a temperature range of 50 °C to
60 °C. A Netzsch DSC 200F3 thermo-analyzer with nitrogen car-
rier gas at a flow rate of 60 mL/min was used to detect the ab-
sorbed or released heat flux during the phase change of W/O
emulsions or salts contained in the original petroleum sludge
and recovered oil samples. A hermetically sealed aluminum cruci-
ble containing 9 mg of the sample and a sealed empty crucible as
the reference cell were subjected to analysis. All heating and cool-
ing rates were set to 5 °C per min according to the recommenda-
tions of Clausse et al. [20]. Samples were heated to 50 °C, where
they were held for 5 min to enable better contact with the crucible
and ensure a uniform temperature distribution within the sample.
The sample was then cooled down with liquid nitrogen coolant to
60 °C and reheated to 20 °C.
3. Results and discussion
3.1. Primary properties of the sludge samples
The primary compositions of three different petroleum sludge
samples are shown in Table 1. The compositions differed according
to the production source and storage conditions. All samples con-
tained water/oil/solid phases with different ratios. Petroleum
sludge ZS was a typical water-in-oil emulsion containing very
small portions of solid particles. Sample NS contained 20.7% solids
as a result of mixing with mechanical impurities (such as sand,
scrap iron, and soil particles) during cleaning of the oil tank. Sam-
ple YS contained the highest content of solids (52.4%), which was
mainly attributed to the complicated composition of the stored
sludge. Additionally, the heating value was found to be propor-
tional to the oil content. Finally, SARA analysis indicated that ZS
had the highest concentration of resins and asphaltenes.
Table 1
Main properties of the studied sludge samples.
ZS NS YS
Heating value (kJ/kg) 28194.6 24360.0 16186.8
Water by distillation/wt (%) 33.5 20.2 16.3
Oil by solvent extraction/wt (%) 65.0 59.1 31.3
Solid residues/wt (%) 1.5 20.7 52.4
SARA analysis/wt (%)
Saturates 23.8 42.1 37.2
Aromatics 25.0 30.9 35.7
Resins 32.6 12.7 19.0
Asphaltenes 17.8 14.3 8.1
216 Q. Huang et al. / Fuel 118 (2014) 214–219
Fig. 1. DSC thermogram of original ZS, oil extracted from ZS, and centrifugation-
treated ZS with a cooling/heating rate of 5 °C/min.
Fig. 2. DSC thermogram of original NS, oil extracted from NS, and centrifugation-
treated NS with a cooling/heating rate of 5 °C/min.
Fig. 3. DSC thermogram of original YS, oil extracted from YS, and centrifugation-
treated YS with a cooling/heating rate of 5 °C/min.
3.2. Freezing behavior of emulsified water in petroleum sludge
DSC thermograms of ZS, NS, and YS petroleum sludge samples
are shown in Figs. 1–3, respectively. The main melting and solidi-
fication peak temperatures for each sample are also indicated in
the corresponding figures.
The DSC curve of the original ZS sample overlaps well with
that of the centrifuged sample. As shown in Fig. 1, there was only
one exothermic signal throughout the entire cooling period, and
the sole Gaussian shaped peak located at 43.5 °C accounts for
solidification of the emulsified water droplets in ZS. The nucle-
ation temperature was much lower than the ice-water equilib-
rium temperature because overcooling is required for emulsified
water droplets to form ice particles [18]. Because the profile of
this peak is very similar to that of other reported W/O emulsions
with uniform water droplets, it is likely that the size distribution
of the water droplets in the ZS sample are relatively narrow
[19,20,22].
The cooling part of the NS DSC curve was completely different
from that of the ZS sample. As shown in Fig. 2, crystallization of
the NS sample starts at around 13 °C and is followed by several
small peaks and one sharp large peak at 23.6 °C. When the sam-
ple was decreased to 29.3 °C, another peak appeared. Previous
investigations of W/O emulsions have revealed that smaller water
droplets are associated with lower solidification temperatures
[18]. Accordingly, these asymmetrical exothermic peaks can be
considered the product of several individual Gaussian-shaped
peaks that each reflects water droplets with a similar size. The
peak at around 44.0 °C is consistent with the same peak in
Fig. 1, accounting for the crystallization of fine water droplets.
After centrifugation, the overall specific heat-release rate near
13 °C increased significantly. These findings indicated that cen-
trifugation caused some small droplets to merge together to form
large droplets.
The heat-releasing nature of the YS sludge sample when it was
cooled to 60 °C was similar to that of NS, except that only two
smooth peaks appeared and the shape of these peaks were broader
than those of NS owing to crystallization of the different- sized
droplets. It should also be noted that, after centrifugation, the heat
flux during the phase change became much stronger, especially for
the YS sample. This occurred because removal of most solid parti-
cles to the bottom layer and increased water content in the upper
layer will increase the specific heat-releasing rate. This phenome-
non explains the almost overlapped DSC curves for the ZS sample
before and after centrifugation treatment due to the relatively
low solid particle concentration. Overall, these findings indicate
that, for petroleum sludge YS, mechanical centrifugation is essen-
tial to remove solid particles before further treatment because of
the high concentration of solid particles. Moreover, the DSC curves
for chemically extracted oil samples shown in Figs. 1–3 demon-
strate that, after Soxhlet extraction, water droplets were removed
completely, making the recovered hydrocarbons very suitable for
chemical use.
3.3. Water content deduced from DSC analysis
Rapid and accurate measurement of the water content and its
properties is of great importance to determining the optimal petro-
leum sludge treatment process. According to the DSC principle, the
total heat absorbed by frozen water during melting within emul-
sion can be used to deduce the total water content w  (%): [23]
mw
 ¼
w ; ð1Þ
ms
where mw (g) is the weight of the water in the sludge sample, ms (g)
is the weight of the sludge sample, and mw is obtained from:
 Q. Huang et al. / Fuel 118 (2014) 214–219 217

Qw where n(Di) is the number of water droplets with diameter Di and q

mw ¼ ; ð2Þ
Hf is the density of water. According to Eqs. (3), (5), and (7), m(Di), the
weight of the water droplet with diameter Di, can be formulated as:
where Qw (J) is the total heat absorbed by the sample during ice
melting and Hf(J/g) is the specific melting enthalpy of frozen water. 4pðDi =2Þ3 ms  Dt i  qi
Hf is considered to be unchanged with temperature; therefore, Qw mðDi Þ ¼ nðDi Þ  q  ¼ : ð8Þ
3 Hf
and Hf can be obtained from the results of DSC by numerical inte-
gration as follows: Additionally, with
Z tb X
i¼N DT i ¼ k  Dt i ; ð9Þ
Q w ¼ ms  qw ¼ ms  q_  dt ¼ ms  Dt i  q_ i ð3Þ
ta i¼1
n(Di) can be obtained from

Z 6  DT i  qi  ms
tb X
i¼N nðDi Þ ¼ ; ð10Þ
Hf ¼ q_  dt ¼ Dti  q_ i ð4Þ q  Hf  k  p  ½exp35=ðT i þ10Þ 3
ta i¼1
where, k is the cooling rate.
where qw (J/g) listed in Table 2 is the specific heat absorbed during Figs. 4–6 illustrate the water size distribution of water droplets
melting, ta and tb are the beginning and ending time of melting dur- in three sludge samples determined according to Eqs. (8) and (10).
ing DSC analysis with a known heating rate, Dt i is the numerical Petroleum sludge ZS was found to have relatively uniform and
integration interval, i.e., i = 1 ti = ta and i = N t = tb, qi (W/g) is the small water droplets with a diameter of 2.7–3.3 lm. Sample NS
heat flux at time ti. Thus, the water content w  of the petroleum showed bimodal distribution with two main groups centered at
sludge is described as: 3 lm and 6 lm, respectively, according to their number density.
mw qw The size distribution profile for the droplets in sample YS was sim-
 ¼
w ¼ ð5Þ ilar to that of NS, except for the larger density of small droplets
ms Hf
near 3 lm.
Based on experimental calculation, the fusion enthalpy Hf was The water content in recovered hydrocarbon resources is very
determined and set as 233 J/g. The water contents deduced from important to their reuse. For W/O emulsions, smaller water drop-
Eq. (5) for the three different samples are given in Table 2. lets result in a more difficult dewatering process. To assess the ef-
The water content values in Table 2 agree well with the data in fects of centrifugation on water droplets, the water droplet size
Table 1, which were determined by the standard method. The rel- before and after centrifugation treatment with respect to the
ative deviation between both methods was 1.94% for NS, 5.07% for weight fraction was evaluated (Table 3).
YS, and 8.89% for ZS. Based on these findings, when compared with After centrifugation, the mean size of the water droplets in NS
distillation, which is time consuming and involves toxic aromatic and YS increased. This occurred because large water droplets will
solvents, DSC analysis provides a rapid, clean, and efficient method be dragged into the sludge, and small droplets in the path of the
to determine the water content from petroleum sludge directly. larger droplets will be merged during centrifugation. However,
Moreover, distillation and chemical methods are incapable of the water droplets in the original ZS samples were so small that
retrieving other information that can be determined by DSC, such the centrifugal force was not sufficient to overcome the oil–water
as the size distribution of the emulsified water droplets. interfacial tension; therefore, the particles size distribution of ZS
was almost completely unchanged after centrifugation.
3.4. Determination of water droplets size distribution from DSC Petroleum sludge ZS is a typical tank bottom sludge with a high
analysis ratio of asphaltenes, which are considered to be natural emulsifi-
ers. The emulsification effect makes water droplets in the sludge
According to previous studies, the water droplets in W/O emul- very stable; accordingly, de-emulsification pre-treatment by meth-
sions usually have different sizes. Based on the thermal equilib- ods such as ultrasonic irradiation [12,24], freeze/thawing [25], or
rium principle, Clausse et al. [19] suggested an exponential electrical treatment [26] is required to decrease the water content
equation to describe the relationship between droplet radiuses in hydrocarbon resources recovered from ZS.
based on crystallization temperature. Their fitting method was em-
ployed in present study as shown in Eq. (6):
 
35
Di ¼ exp ; ð6Þ
T i þ 10
where the droplet diameter D was determined from the droplet
freezing temperature T, which can be obtained by DSC analysis at
a known cooling rate.
When the water droplet size is known, the weight of a spherical
water drop can be determined as follows:
" #
X
i¼N
4pðDi =2Þ3
mw ¼ nðDi Þ  q  ; ð7Þ
i¼1
3

Table 2
Water content deduced from DSC.

Melting peak ZS-‘b’ NS-‘e’ YS-‘d’

Peak area qw (J/g) 85 48 40
Water content (wt%) 36.48 20.60 17.17 Fig. 4. Weight and number percentage of water content in ZS with respect to
droplet size.
218 Q. Huang et al. / Fuel 118 (2014) 214–219

Fig. 5. Weight and number percentage of water content in NS with respect to Fig. 7. DSC thermogram of deionized water and wastewater from the same
droplet size. reservoir of NS with a cooling/heating rate of 5 °C/min.

and 4.6 °C, respectively, and no other heat flux peaks were ob-
served. However, the presence of dissolved salt in the wastewater
sample inhibited the crystallization of water, which caused the
heat flux-releasing peaks for freezing and melting to shift to
21.1 °C and 1.7 °C, respectively. Clausse et al. [17,18] reported
that melting temperature can be used as a qualitative estimator
of the concentration of dissolved salt in W/O emulsions, with high-
er salt ratios being associated with lower melting points. Based on
his argument and considering the heat absorption flux peaks
shown in Figs. 1(b), 2(e), and 3(d), the salt content of sample NS
is larger than that for YS, while ZS has the lowest salt content.
Similar to the heat absorbing peaks observed for NS and YS, a
small heat absorbing peak was observed at around 23 °C for the
wastewater sample. These peaks are believed to be associated with
the melting process of eutectic salt-water mixtures, namely H2O–
NaCl and H2O–NaCl–KCl. These peaks provide further evidence of
the existence of salt in petroleum sludge. Moreover, the value of
the specific heat released during eutectic melting is proportional
Fig. 6. Weight and number percentage of water content in YS with respect to to shifts in temperature, with higher heat peaks being associated
droplet size. with larger temperature shifts or higher salt content.
The hydrocarbon resources recovered from petroleum sludge
are expected to be used as chemical material or combustion fuel.
Table 3
To eliminate the unfavorable effects caused by salt species, desalt-
Size distribution of water droplets before and after centrifugation.
ing treatment is required. DSC analysis provides a simple method
ZSa ZSb NSa NSb YSa YSb to obtain salt information that can be used to guide the desalina-
<3.5 (lm/wt%) 100.0 100.0 20.0 14.9 42.5 34.6 tion process. For example, sludge NS contains a large aqueous
3.5–10.0 (lm/wt%) 0 0 72.1 75.1 50.0 54.7 phase, yet relatively low levels of emulsified water droplets; there-
>10.0 (lm/wt%) 0 0 7.9 10.0 7.5 10.7
fore, desalting and dewatering of this sludge can be achieved at the
a
Original sample. same time through ultrasonic irradiation [20,24].
b
Centrifugation-treated sample.

4. Conclusion

3.5. Identification of the salt content
As discussed above, salt present in recovered oil may decrease
the efficiency of catalysts and cause facility corrosion and second-
ary pollution. However, there is currently no rapid or efficient
method to identify the presence of salt in petroleum sludge. As
shown in Figs. 1–3, when the samples were reheated to room tem-
perature, their melting temperatures were found to vary slightly.
Therefore, two other samples, one of deionized bulk water and an-
other of NS petroleum tank wastewater (which contained dis-
solved alkali salts), were subjected to DSC analysis under the
same conditions for comparison. As shown in Fig. 7, the deionized
water showed heat flux peaks for freezing and melting at 18.8 °C
Characterization of emulsified water and identification of salt in
petroleum sludge is very important and useful for guiding and
optimizing treatment processes. In this study, three different types
of petroleum sludge before and after centrifugation were evaluated
by DSC, and a new mathematic equation was proposed to relate
water droplet size to freezing temperature. The results indicate
that different water droplets contained in the sludge have different
freezing temperatures, with smaller sizes being associated with
lower freezing temperatures. For petroleum sludge collected di-
rectly from a crude oil tank, the natural emulsification effect of
asphaltenes causes the size of the water droplets in the sludge to
be uniform and small. The size distributions of the water droplets
in sludge samples collected from mixtures of petroleum wastewa-
 Q. Huang et al. / Fuel 118 (2014) 214–219
ter and sludge were much broader, and the droplets merged to
form larger ones during centrifugation. The small heat flux absorb-
ing peaks near 23 °C generated during the heating phase along
with the decreased melting temperature of frozen water droplets
could be used to identify the existence of salt in the sludge.
DSC enabled qualitative and quantitative analysis of the emul-
sified water in petroleum sludge. This technique has the advantage
of providing important information within a single measurement,
including the emulsion droplets size distribution, stability of W/O
emulsion in oily sludge, total amount of water, presence of salt,
and the removal rate of solids after treatment.
Acknowledgments
We are grateful to the National Basic Research Program of China
(973 Program) (Grant No. 2011CB201500), National Science &
Technology Pillar Program (No. 2012BAB09B03), National High
Technology Research and Development Program (No.
2012AA063505), and the Creative Team Project of Solid Waste
Treatment of Zhejiang Province (A2009R50049) for their financial
support.
References
[1] da Silva LJ, Alves FC, de Franca FP. A review of the technological solutions for
the treatment of oily sludges from petroleum refineries. Waste Manag Res
2012;30:1016–30.
[2] Wang SJ, Yan ZG, Guo GL, Lu G, Wang QH, Li FS. Ecotoxicity assessment of aged
petroleum sludge using a suite of effects-based end points in earthworm
Eisenia fetida. Environ Monit Assess 2010;169:417–28.
[3] Salanitro JP, Dorn PB, Huesemann MH, Moore KO, Rhodes IA, Jackson LMR,
et al. Crude oil hydrocarbon bioremediation and soil ecotoxicity assessment.
Environ Sci Technol 1997;31:1769–76.
[4] Diya’uddeen BH, Daud WMAW, Abdul Aziz AR. Treatment technologies for
petroleum refinery effluents: a review. Process Saf Environ Prot
2011;89:95–105.
[5] Elasheva OM, Lubsandorzhieva LK, Smirnov IN, Fedorova EV. Entrainment of
drainage emulsions and petroleum sludges in stock crude oil. Chem Technol
Fuels Oils 2003;39:151–4.
[6] Ávila-Chávez MA, Eustaquio-Rincón R, Reza J, Trejo A. Extraction of
hydrocarbons from crude oil tank bottom sludges using supercritical ethane.
Sep Sci Technol 2007;42:2327–45.
[7] Zubaidy EAH, Abouelnasr DM. Fuel recovery from waste oily sludge using
solvent extraction. Process Saf Environ Prot 2010;88:318–26.
219
[8] Gallego J, García-Martínez M, Llamas J, Belloch C, Peláez A, Sánchez J.
Biodegradation of oil tank bottom sludge using microbial consortia.
Biodegradation 2007;18:269–81.
[9] Koolivand A, Naddafi K, Nabizadeh R, Nasseri S, Jafari AJ, Yunesian M, et al.
Biodegradation of petroleum hydrocarbons of bottom sludge from crude oil
storage tanks by in-vessel composting. Toxicol Environ Chem 2012;95:101–9.
[10] Shie JL, Chang CY, Lin JP, Wu CH, Lee DJ. Resources recovery of oil sludge by
pyrolysis: kinetics study. J Chem Technol Biotechnol 2000;75:443–50.
[11] Wang Z, Guo Q, Liu X, Cao C. Low temperature pyrolysis characteristics of oil
sludge under various heating conditions. Energy Fuels 2007;21:957–62.
[12] Jin Y, Zheng X, Chu X, Chi Y, Yan J, Cen K. Oil recovery from oil sludge through
combined ultrasound and thermochemical cleaning treatment. Ind Eng Chem
Res 2012;51:9213–7.
[13] Goncalves MLA, Teixeira MAG, Pereira RCL, Mercury RLP, Matos JR.
Contribution of thermal analysis for characterization of asphaltenes from
Brazilian crude oil. J Therm Anal Calorim 2001;64:697–706.
[14] Goncalves MLA, da Mota DAP, Teixeira AMRF, Teixeira MAG.
Thermogravimetric investigation on prediction of thermal behavior of
petroleum distillation residues. J Therm Anal Calorim 2005;80:81–6.
[15] Kok MV, Karacan O, Pamir R. Kinetic analysis of oxidation behavior of crude oil
SARA constituents. Energy Fuels 1998;12:580–8.
[16] Zanier A. Application of modulated temperature DSC to distillate fuels and
lubricating greases. J Therm Anal Calorim 1998;54:381–90.
[17] Clausse D, Pezron I, Gauthier A. Water transfer in mixed water-in-oil
emulsions studied by differential scanning calorimetry. Fluid Phase
Equilibria 1995;110:137–50.
[18] Clausse D. Thermal behaviour of emulsions studied by differential scanning
calorimetry. J Therm Anal Calorim 1998;51:191–201.
[19] Clausse D, Gomez F, Dalmazzone C, Noik C. A method for the characterization
of emulsions, thermogranulometry: application to water-in-crude oil
emulsion. J Colloid Interface Sci 2005;287:694–703.
[20] Clausse D, Gomez F, Pezron I, Komunjer L, Dalmazzone C. Morphology
characterization of emulsions by differential scanning calorimetry. Adv Colloid
Interface Sci 2005;117:59–74.
[21] Avendano-Gomez JR, Grossiord JL, Clausse D. Study of mass transfer in oil-
water-oil multiple emulsions by differential scanning calorimetry. J Colloid
Interface Sci 2005;290:533–45.
[22] Díaz-Ponce JA, Flores EA, Lopez-Ortega A, Hernández-Cortez JG, Estrada A,
Castro LV, et al. Differential scanning calorimetry characterization of water-in-
oil emulsions from Mexican crude oils. J Therm Anal Calorim
2010;102:899–906.
[23] Lee DJ, Lee SF. Measurement of bound water content in sludge: the use of
differential scanning calorimetry (DSC). J Chem Technol Biotechnol
1995;62:359–65.
[24] Ye G, Lu X, Han P, Peng F, Wang Y, Shen X. Application of ultrasound on crude
oil pretreatment. Chem Eng Process 2008;47:2346–50.
[25] Chen G, He G. Separation of water and oil from water-in-oil emulsion by
freeze/thaw method. Sep Purif Technol 2003:3183–9.
[26] Elektorowicz M, Habibi S, Chifrina R. Effect of electrical potential on the
electro-demulsification of oily sludge. J Colloid Interface Sci 2006;295:535–41.