SPE 105765
Thermochemical Process To Remove Sludge From Storage Tanks
Nelson O. Rocha, Carlos N. Khalil, Lcia C.F. Leite, and Andre M. Goja, Petrobras
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 28 February2 March 2007.
This paper was selected for presentation by an SPE Program Committee following review of
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Abstract
The periodic cleaning of the bottom of crude oil storage
tanks in vessels, terminals and refineries has become a
big problem for industrial maintenance, principally due to
the temporary inoperability of the equipment and the
high environmental impact caused by the conventional
treatments used. The storage of crude oil in large tanks
invariably creates a gradual deposition process of
organic sediments of high molecular weight.
PETROBRAS has developed a thermochemical method
aimed at removing wax deposits in submersed oil
pipelines, wax damage in production reservoirs and
petroleum sludge removal from storage tanks.
This work presents the chemical treatment performed
inside an oil storage tank located onboard an oil tanker
as well as the laboratory methodology for the organic
deposit physical-chemical characterization, kinetics of
reaction, physical simulation, treatment dimensioning
and operational treatment, aimed at the removal of 800
3
M of organic deposit.
The thermochemical method consists of a chemical
reaction between two nitrogen salts that produce a
strong exothermic chemical reaction. The heat produced
by the reaction, together with the turbulence due to the
generation of a large volume of nitrogen and the
solvency, dispersed the initially solid compacted sludge
at the bottom of the tank. The heat of the solution,
estimated at 90oC, in contact with the sludge, irreversibly
melted the organic fractions according to the previously
studied phases diagram.
The method demonstrated itself to be efficient, safe and
of low cost, when compared to existing classic methods.
The process financial balance showed that the cost of
the oil recovered from the organic deposit paid for the
investment in chemical reagents and operational
facilities.
Introduction
Since 1990, PETROBRAS has been performing
thermochemical treatment aimed at the removal of oil
sludge in storage tanks for oil and its derivatives,
desalinators, separator vessels, flotators and related
equipment.
The oil sludge found at the bottom of storage tanks for
oil and its derivates is defined as a multiphase water-oil-
solid system with high stability, possessing a semi-solid
physical state, produced from the gradual process of the
sedimentation of heavy oil fractions, when submitted to
the classic storage conditions. It appears in the form of
an emulsion, varying in consistency, density, thickness
and composition across the whole bottom of the tank.
Inorganic solids originally present in the crude oil, such
as clay, silica, calcite as well as the residues produced
from corrosion, contribute also to the process, bringing
more hardness and higher density to the deposit. The
compacting of the sediment, associated with the
degradation of the organic compounds during the
storage, leads to the formation of a thick layer of sludge
which is difficult to remove.
The thermochemical method, as well as the other
methods (mechanical cleaning, centrifuging, robotic
cleaning and solvent dilution) possesses some
application limitations. The described method becomes
more efficient when the sludges are of a predominately
wax nature possessing low percentages of water and do
not have contaminating agents that provoke the
alkalinization of the solution. The uniformity of the
deposit at the bottom of the tank is also a prerequisite for
the execution of the treatment. Furthermore, the
significant differences between the various kinds of
sludges, associated with their formation process,
implicate the necessity to establish individual
procedures, principally regarding the selection or mixture
of the solvents. For this reason it is fundamental to know
the sludge characteristics to define the best form of
treatment and removal.
2 SPE 105765

Case Histories available at the industrial unit and it is used as an acidic

activator agent. The Urucu oil was used as an organic
Tanks 1 2 3 4 5 6 7 8 solvent due to the chemical similarity of the sludge and
Sludge treated (M3) 1000 80 1150 20 20 250 900 1000 its availability in the region. The process applied in tanks
Cost of treatment 55 100 55 45 110 80 70 150
3
seeks to promote the irreversible melting of the sludge
(U$ / M of sludge)
through the simultaneous effects of heat from the
Cost of conventional treatment 200 600 200 200 600 500 500 600
3
(U$ / M sludge)
exothermic reaction in an aqueous solution, turbulence,
Removal efficiency (%) 60 80 56 100 100 60 100 60
floatation due to the in-situ generation of nitrogen and
solvency due to the prior addition of the organic solvent
and special additives.

Table 1- Previous treatment histories in storage tanks
Scenario
An oil storage tank with a capacity of 7000 M3 on the oil
tanker Presidente Floriano located on the Rio Negro,
near the city of Manaus, Brazilian Amazon region, had
been used for all its useful life for the storage of crude oil
and the thermochemical treatment for the removal of
sludge had the objective of recuperating the 79% of oil
present in the sludge, as well as the subsequent periodic
maintenance at the bottom of the tank.
The ships tank had these dimensions: 36 M long, 12 M
wide and 18 M high. The depth of the sludge inside the
tank was 1.85 M equivalent to 800 M3 of sludge. The
bottom of the tank is in permanent contact with the water
of the Rio Negro with a temperature during the treatment
period of 30oC. The side walls are immersed in a water
tank at 40oC.
Description of Methodology
PETROBRAS had originally developed a
thermochemical method to remove wax deposits in
submersed oil pipelines 1 used for the production and
transportation of crude oil and also for the removal of
wax damage in production reservoirs 2,3. The method
was based on the chemical reaction, extremely
exothermic, between two nitrogen salts, in precise
chemical reactive proportions and catalytic acid
condition. Large volumes of nitrogen and heat are
obtained in a controlled reaction that is correctly
combined with an organic solvent, producing an
irreversible melting of the organic deposit.
In the same way this thermochemical method, with some
modifications, can be used in the interior of industrial
vessels such as storage tanks and desalinators in
industrial plants with the objective of removing crude oil
sludges as this chemical reaction shows:
H+
2 NaNO2 + (NH4)2 SO4 2 N2 + Na2SO4 + 4 H2O (1)
The organic solvent was chosen in agreement with the
chemical nature of the sludge, the lowest cost products
The operational sequence for the sludge removal
treatment initially consisted of the dilution of a previously
selected chemical dispersant, followed by its transfer to
a tank maintaining the system in circulation.
Subsequently a saline solution was made and this was
then transferred to the tank, thus forming an
intermediate phase between the sludge and the solvent.
The chemical reaction is activated with the addition of
the acid through the top of the tank in order to guarantee
the total activation of the reaction. This catalyst changes
the pH of the solution from slightly alkaline to slightly
acidic when the chemical reaction is activated. Special
additives were added to improve the wax dispersion and
avoid the formation of stable emulsions. 4,5.
The floatation induced by the nitrogen generated in-situ
promotes the migration of the sludges oily melting
phase to the solvent. The separation phases occur (oil,
water and inorganic solids) some 2 or 3 hours after the
chemical reaction has completed. Its important to
mention that the final condition must be irreversible
melting of the organic phase.
Some 2 or 3 hours after the reaction development, there
is a segregation of:
water phase (sodium sulfate solution + original
sludge water)
oil phase (mixture of Urucu oil + organic fraction
of the sludge) and
the inorganic solid phase (resulting from the
liberation of inorganic solids originally present in
the sludge).
The operational safety during the thermochemical
treatment is reinforced by the saturated formation of an
inert atmosphere in the tank by the nitrogen gas
generated by the chemical reaction. The perfect
separation between the aqueous saline phase, located
at the bottom of the tank, and the oil phase, located in
the upper part of the tank, at the end of the treatment,
guarantees the maximum recuperation of the organic
compounds present in the sludge.
The most significant advantages of the sludge treatment
and removal method are:
the considerable reduction of the inoperable time
3 SPE 105765

of the tank; Water Characteristics

the elimination of the presence of people in the
tank interior;
the maximum recuperation of the organic
fraction from the sludge and
From the water separated from the sludge by centrifuge
the pH was determined in order to know its compatibility
with the aqueous thermochemical solution.
Melting Point

the formation of an inert atmosphere in the tank The melting point of the sample corresponds to the
during the treatment. minimum temperature at which it is still possible to make
the sample flow through an external action. This
arrangement allows the detection of the slightest
Laboratory Methodology movement on the surface of the sample. The procedure
performed followed the ASTM D97 method
Sampling recommendations. This action allows the thermal
conditions to be known of the original sludge movement
properties and after the organic solvent dispersion and
The organic deposit sampling is a fundamental stage for
the reversibility of the mixture from the phase diagram.
the correct dimensioning of the reagent quantities
necessary for the total melting and recuperation of the
WAT
deposit in the liquid phase. Approximately 20 samples of
about 1 kg in weight were collected, from different points
The Differential Scanning Calorimetric (DSC) technique
and depths of the sludge in the tank interior.
applied allowed the transition temperature to be
determined of the wax fraction of the oil between the
The samples were duly homogenized and submitted to
liquid and solid phases. A complete thermogram reveals
tests to determine the percentages of water, oil and
the enthalpy variation in function of the temperature at
inorganic solids present in each sample. The fractions
each moment of the process.
resulting from the tests were characterized through
physical-chemical tests. The original sludge samples
The equipment (Perkin Elmer, model DSC-3) permitted
were also characterized for their melting point and their
the determination of the WAT value that corresponds to
WAT (Wax Appearance Temperature) 5. Laboratory
the point on the thermogram where the formation of the
simulations were made with various combinations of
first crystals occurred in the liquid phase of the sample,
thermochemical aqueous solutions, organic solvents and
which involved a sudden enthalpy variation in the
special dispersant additives with the objective of making
solution. This point can only be easily recognized in
a proposal of a sludge removal treatment for the tank.
mixtures that possess a reasonable percentage of wax
compounds that are exactly those which have the
Measurement of Percentages of water / oil / solids
biggest enthalpy variation value at the transition of liquid-
solid.
Solvents were used to make the extraction in order to
quantify the percentages of water, oil and inorganic
In the same way that the melting point test, this
compounds.
experiment permitted the determination of the WAT
reduction in function of the sludge dispersion in a given
Oil Characterization
organic solvent.
The oil present in the sludge was characterized by
Kinetics of the reaction
chromatography, the percentages of saturates,
aromatics, resins and asphaltenes (SARA). These
Based on the enthalpy fusion results, the necessary
results guided the selection of an organic solvent
quantities of the chemical reagents were determined to
chemically compatible with the oil fraction present in the
produce the required thermal energy for the melting of
sludge.
the oil sludge as well as the velocity of the reaction in the
tank interior. The kinetic reaction data is obtained by a
Solid Characteristics
system composed of a stainless steel reservoir, capacity
350 ml, with a 0.6 mm thick Teflon cup inside it.
The inorganic solids resulting from the solvent
extractions were then submitted to fluorescence (FRX)
The tank has J type thermopar temperature sensors that
and diffractometry (DRX) tests in order to know the
make contact with the fluid test. The temperature
contaminants that could possibly interfere with the
parameters in function of time were obtained in a data
evolution of the reaction.
acquisition system.
4 SPE 105765

Phases diagram Experiment Results

The phases diagram graph permits the determination of Determination of percentage of water, oil and solid
the solvent quantity necessary to incorporate the melted
sludge oily fraction in an irreversible form after the return Table 2 shows the average result obtained in the
to the ambient thermal conditions. characterization tests of the various sludge samples.

As the phases diagram shows in figure 1, the initial

sludge condition, at a temperature of 25C is Oil (%) Water (%) Inorganics (%)
characterized by the in-situ temperature and by the lack 79 17 4
of organic solvent. Once the reaction is activated, there
is a previously calculated thermal propagation in the tank Table 2- Results of determination of percentages of
interior. The ternary system of nitrogen / water / solvent water, oil and solids in the sludge
permits a better melting of the sludge, in addition to the
heat, originating from the exothermic reaction process, Characteristics of the oil
thus increasing the temperature of the tank interior,
melting the organic fractions by thermal transfer, that Table 3 shows the chromatography method average
invariably exceeds the corresponding melting point results of the oil removed from the sludge.
temperature.
Saturates Aromatics Resins Asphaltenes
Once the sludges organic fraction has melted, the
72 21 5 2
solvent phase is incorporated into it, thus causing a
slight temperature reduction in the system. When the
chemical reaction has finished the effluents were Table 3- Chromatography average results
removed from the tank.
Characteristics of the inorganic solids
Physical Chemical Simulation
The identification test of crystalline compounds by
Based on the sludges chemical characteristics the diffractometry shows that the samples contain calcium
samples were treated with different solvent and aqueous sulfate (CaSO4) and ferrous oxide (Fe2O3).
nitrogen solution compounds and dispersant additives in
a glass jar with dimensions similar to the tank. The Table 4 shows the average results of semi-quantitative
treatment test further considered the accompanying of analyses of the elements present in the inorganic solid
the evolution of the chemical reaction, where the residue separated from the sludge and analyzed by
increase in temperature is evaluated, sludge dispersion fluorescence.
in the solvent, separation of the phases and the
irreversibility of the melting process.
Analyzed Result (%)
sodium 12
magnesium 2
calcium 11
aluminum 1
silica 4
sulfur 31
ferrous 27
zinc 2

Table 4 - Results of semi-quantitative analysis by

fluorescence

Characteristics of the water

The water originally present in the sludge, separated by

centrifuge, indicated a pH slightly alkaline (pH =8).

WAT

Table 5 shows the average results to determine the

Figure 1 Phases diagram of the process
melting point in the original sludge samples.
5 SPE 105765

WAT Enthalpy of Enthalpy of

(C) Crystallization (J / g) Fusion (J / g)
72 42 40

Table 5- Results of the WAT of the original samples

Kinetics of the reaction

The kinetics of the reaction were determined in adiabatic

conditions where the evolution of the temperature and
pH of the system where accompanied.

Figure 2 shows the thermal evolution of the aqueous

solution with a concentration of 4 mol / L in function of
the reduction of pH during the chemical reaction.
Figure 3: Kinetics of the reaction under the action of the
ions Fe3+.

Phases diagram
6.00
90
Table 6 shows the reduction of the melting point in
function of the dilution of the sludge using Urucu oil and
TEMPERATURE ( C )

diesel. It was concluded that a relation of 1 part sludge

4.00
to 2 parts of solvent was sufficient for the total dispersion
60 of the organic fractions in the sludge in the solvent in an
pH

TEMPERATURE
pH
irreversible way at 25C.

30 2.00 Sludge Oil Melting Point with Melting Point with

Diesel (C) Urucu Oil (C)
1 0 72 72
1 1 52 48
0 0.00
1 2 48 46
1 3 44 44
0 30 60 90
1 4 43 44
TIME (minutes)

Figure 2: Kinetics of the aqueous reaction
The influence of the contaminants in the chemical
reaction activation was also studied. It was concluded
that the two reagents could not remain together for a
period of time of more than 2 hours. This was due
principally to the iron from the tank walls that changed
into ferrous hydroxide reducing the pH and starting the
reaction at an inopportune moment as shown in the
graph of figure 3
Table 6: Variation of melting point in function of the
sludge and solvent percentage.
Simulation of the reaction
A series of experiments were made with the sludge in a
Pyrex glass container with proportional dimensions to
the tank as shown in figures 4 to 8. Based on the results
of the phases diagram, a percentage of 1 part sludge to
2 parts solvent (Urucu oil) was used. The first
experiment showed that the nitrogen produced from the
reaction provoked intense foam that could exceed the
limits of the tank. Therefore, a silicone additive was used
to minimize the foam formation. In addition to this,
surfactants and wax dispersant agents were added. The
sequence of photos below show the thermochemical
action in the sludge collected from the tanker. It can be
observed that the experimental proportions, when later
converted to the real situation, the sludge was totally
melted and irreversibly incorporated into the solvent. In
the final condition the melted deposit, which is
incorporated into the solvent in an irreversible process,
appeared in the upper part of the glass container and the
6 SPE 105765

aqueous solution reaction product of sodium sulfate with

a neutral pH, remained in the lower part.

Figure 7: Melting of the deposit and incorporation into

the solvent for floatation.
Figure 4: Glass container with the organic deposit in its
solid state stuck to the bottom.

Figure 8: Final condition: deposit melted and

incorporated into the solvent in the upper part and the
Figure 5: Transfer of the solvent and aqueous solution reaction product sodium sulfate aqueous solution with
into the glass container. neutral pH in the lower part.

Dimensioning

Formulation

Based on the tank dimensions, the sludge mass and the

results of the experiments, the treatment was
dimensioned as shown below:

Data Values
Sludge volume 800 M3
Saline solution volume 160 M3
Urucu oil volume 1 500 M3
Antifoam volume 1 M3
Dispersant volume 2 M3
Figure 6: Exothermic chemical reaction development. Thermal Capacity 130 Kcal / L
Maximum Temperature 91C
Specific Heat 4190 J / Kg C
7 SPE 105765

Solution concentration 4 moles / L Applying the values, the temperature balance is 71C. It
Solution pH 7,5 is estimated that at the aqueous phase the temperature
Reaction pH 4,6 reached close to 100 C.
Final pH 7,0
Density 1,2 Kg / L It should be highlighted that this temperature balance in
Thermal Capacity 130 Kcal / L the interior of the tank exceeds the temperature
necessary to melt the sludge with solvent in a proportion
Table 7: Quantities, Chemical and Physical Properties of 1:2 of 48C in agreement with the experiment results
shown in table 6

Thermal Balance of the Process Aspects and Impacts, Health, Safety and Environment
During the agitation of the mixture, temperatures were
registered, inside the tank, of around 40C. All the other The thermochemical method used is characterized by
walls are immersed in a water tank at 40C. The tank the controlled generation of heat and inert gas (nitrogen)
was maintained partially closed with a few vents to allow and having as a saline effluent sub-product (sodium
the nitrogen gas to escape. The external ambient sulfate) free of oil.
temperature was 30 C.
1500 M3 of Urucu oil and 160 M3 of saline solution of 4,0 The solvent used plus the organic fraction recovered
mol / L were added to the tank containing the sludge. from the sludge go into the refining process.
All the treatment procedure, preparation of the fluids,
Properties Sludge Aqueous Urucu activation of the reaction and the recuperation of the
Solution Oil effluents were discussed in detail at the location, with the
Specific Heat 0,65 1,05 0,55 team before beginning of the work. The area was
(Kcal / Kg * C) isolated and the lines and emulsion preparation tanks
Density 0,90 1,20 0,85 were inspected.
(Kg/L)
The process of making the solutions was very carefully
Table 8: Chemical and Physical Properties
monitored. The pH was a fundamental parameter in the
preparation of the fluids. The monitoring of this property
The chemical reaction produced in the aqueous solution
was continuous, in all the stages of the preparation.
is capable of producing 75 kcal/mol of generated
nitrogen. Therefore, for the treatment of a volume of 160 All the team that handled the chemical products wore
M3 of a saline solution with the specified concentration, field uniforms, masks, glasses, rubber gloves, helmets,
around 4,32 E+07 kcal are produced. ear protectors, impermeable apron and boots.

To calculate the heat of the reaction in the specified
concentration in the proposed treatment the performed
reaction was assumed to be 90%. This assumption was
made in order to take into account the heat loss of the
process to the exterior ambient according the equation
(2):
Q solution = 75 kcal / mol. 160 M3. 4 mol / L. 103 L / M3.
0,9 = 4,32 E+07 kcal (2)
The equation below shows the calculation of the thermal
balance of the process.
Q = (cp . . V . T)SGN + (cp . . V . T)SOLVENT + (cp . .
V . T)SLUDGE (3)
Where:
Q heat produced by the chemical reaction in kcal;
cp calorific capacity in kcal / kg.C;
density in t / M3;
V volume in M3 ;
T Thermal difference between the ambient
temperature and the balance in C.
All care was taken to not block any of the lines containing
the aqueous solution to avoid possible rupture. All the
tanks and lines were washed after the treatment to avoid
any undesirable reactions in some point that had solution
potentially reactive.
Results
It is estimated that the recuperation of the effluents
delivered the quantity of the oil used as a solvent
together with the oil contained in the sludge, the aqueous
volume produced from the chemical reaction (sodium
sulfate) there remaining in the bottom of the tank
inorganic residues.
The cost of the oil recuperated exceeded the investment
spent in the purchase of chemical reagents and
operational facilities.
Acknowledgements
The authors would like to thank PETROBRAS for
permission to publish the paper and Mr. Roger Wilkinson
for translation and review of the text.
8 SPE 105765
Conclusions
PETROBRAS Research & Development Centre
developed an environmentally friendly thermochemical
method to remove oil sludge from storage tanks or other
recipients of a treatment based on the strong exothermic
reaction between two nitrogen salts. In this condition
there are obtained large quantities of nitrogen and heat
in addition to turbulence, a flotation effect combined with
an organic solvent. The process promotes the
irreversible melting of the organic deposit and
recuperated oil goes to the refinery.
Therefore the process combines advantages of zero
cost because the oil obtained is recuperated and it
eliminates the presence of people inside the tank, and in
addition renders inert the atmosphere inside the tank
during the treatment.
The method reduces the time for the execution of
equipment maintenance, minimizes environmental
impacts and maximizes aspect of operational safety and
occupational health.
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R.M.: A Thermochemical Process for Wax Damage
Removal - SPE 80266 SPE Symposium on
Oilfield Chemistry, Houston (2003)
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of formation damage associeted to paraffin in
reservoir of the Recncavo Baiano - SPE 37238 -
International Symposium on Oilfield Chemistry, Ohio
(1996)
3. Khalil, C. N. and Rocha, N. O: Controlling Wax
Deposition in Offshore Production Systems -
PETROBRAS Experience IBC Global Conferences
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