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Dr. T. J.

Gunner

The Physical Behaviour of Crude Oil during Transportation


and its Impact upon the Carriage of Crude Oil by Sea

The Physical Behaviour of Crude Oil


Abstract Influencing its Carriage by Sea –
CRUCOGSA
This paper provides an overview of the content,
purpose and findings as a result of a research
This three year research project, undertaken
programme undertaken between 1996 and 1999
between 1996 and 1999, forms the first stage of
into the captioned subject.
a larger research programme entitled The
Marine Transportation of Crude Oil (MATCO).
Crude oil being the most complexed liquid
The project, due to its importance and potential
carried by sea required investigation due to its
findings/impact, was sponsored by a true cross
behavioural characteristics that impact the
section of the Crude Oil transportation industry
efficiency of its transportation, handling and
and interested bodies ranging from
general tanker operations. The research
INTERTANKO to a variety of Oil Companies,
programme broke the subject matter down to the
Government Organisations and individual oil
three phases of crude oil each of which, either
company and independent tanker fleets
on its own or in conjunction with other phases,
create problems onboard tankers. Clearly the
three physical phases are those of the Vapour, Background and Objectives of the
Liquid and Sludge phases. Research

The programme collected both data of diverse The general objectives or goals for the
type/description from the numerous vessels CRUCOGSA project were to determine the
participating in the programme together with physical behaviour of a variety of crude oils
cargo samples of the various types of crude oil whilst being transported such that increased
carried for each voyage. The samples were efficiency can be obtained for industry by
obtained at discrete points throughout the controlling volumetric loss of this diminishing
voyage and discharge of the diverse cargoes and resource. The project would also supply data
were subsequently analised for their physico- that would aid in the control of liquid and
chemical properties. With the analytical vapour pollution to the environment. This, it
information of the various cargoes and the cargo was deemed, would create significant economic
and environmental reports from the vessels, benefit to the oil industry.
researchers can gain an overview as to the
diverse types of behaviour occurring to the The rapid increase in Crude oil value in the 1970's
cargoes during their transportation. and again in 2000 has made industry more
conscious of crude oil cargo losses. It is
Subsequent empirical modelling of a proportion recognised by the industry, who are both
of the data has allowed equations to be created environmentally and fiscally aware, that close
that would assist vessels’ commands to gain an monitoring and measurement of this vital feed
insight into cargo behaviour to assist in decision stock source is important. Previous statistical
making for operational matters. studies supplied some reliable overall guidance to
the industry regarding volumetric loss expectation,
This paper provides the initial information but also derived some broad distributions for the
and models developed as a result of this data populations. Only limited data from scientific
extensive piece of data collection and work. studies undertaken by the industry have been
published regarding the physical behaviour of
crude oils carried by sea. Where such studies Clearly these initial goals were poorly defined for
have been undertaken they were restricted to a the purposes of a research project,
specific crude oil, type of vessel or voyage. notwithstanding the fact that the general
objectives of the research project are clear. The
In order to increase the economics for the project’s goals could not have been more closely
transportation of crude oil by sea the behaviour of defined before adequate preliminary evidence was
the crude oil during its long transportation period available, given the basis of only a short
must be fully understood so that systems, preliminary pilot study, before the commencement
techniques and generally handling behaviour can of the main project.
be modified, where appropriate, to maximise the
receipt of these materials and limit their adverse In the event and at a meeting in October 1997 the
impact on the environment if released during the following objectives of the programme were
transportation period. defined and subsequently accepted by the
Research Review Committee (being
Knowledge of the physico-chemical behaviour of representatives from all the sponsoring entities) as
crude oil being carried aboard a tanker would not objectives that could be achievable from the
only have a significant impact upon the efficient programme. The Objectives became:-
carriage of oils and oil loss control but also supply
data to the general maritime industry for (1) To compile a database of information
assistance in pollution control from tankers. Some that can be reliably accessed to gain information
of the criteria investigated (e.g. viscosity of concerning the behaviour of crude oil during its
diverse crude oils at a variety of temperatures) transportation by sea.
would be of significant value in the decision
making for appropriate oil spill response methods (2) To supply data in a user friendly form
in the event of an oil spill and the prediction of the for vessels’ officers to use when handling and
behaviour and fate of an oil slick. transporting crude oil.

Currently, when tankers are carrying certain crude (3) To investigate the causes or reasons for
oils unheated under certain environmental identified operational difficulties (e.g. pumping,
conditions, tank sludging with 10,000 barrels COW and vapour emissions). This will include
(1600 m3) can occur. Such circumstances can the supply of mathematical models to predict the
occur during the Northern Hemisphere winter required temperature in order to avoid
months and cause exaggerated overall losses precipitation of sludge or attaining a more
(20,000 bbls - 3,200 m3) during the overall efficient washing temperature/programme for
transportation of cargoes. This sludge material closed cycle crude oil washing and, to aid tanker
having emanated from the original crude oil operators with sludge minimisation and
would, if replaced within the original crude oil, conversely with the minimisation of vapour loss
attract a value of approximately U.S.$ 250,000 from over heating.
and reduce the overall loss which could have a
value of $500,000. Likewise with vapour (4) To supply data that will assist with the
emissions, the previously reported loss of gas at modification of current international regulations
about 0.17% of cargo volume seems to where they are believed to be inappropriate for
underestimate preliminary measurements of vessel guidance or use.
between 0.4 and 0.6% for a volatile type of crude
oil. All of the foregoing was achieved by the project
either in full or part. Due to the extensive
With such ongoing monetary losses and the amount of data both of crude oil properties and
associated significant costs in the subsequent voyage cargo and environmental records further
removal of these deposits and cleaning of vessels, projects are being currently undertaken within
more efficient transportation criteria must be made the MATCO programme to utilise and explore
available. the diverse permutations and combinations of
information. These current projects concern Sludge Generating Parameters
both “Vapour Emission Control” (VOCON) and
“Crude Oil Measurement Control” The primary parameter available to a vessel’s
(CRUMECON). In addition other projects have command today for advices is that of the crude
been undertaken using this scope of information, oil’s Pour Point temperature. This parameter is
which include “Abnormal Corrosion to Crude said to record the temperature at which the crude
Oil Cargo Tanks” (CRUCOR), or are under oil, once cooled, is just capable of flow or
planning, “Effective Crude Oil Washing” “being poured”. Thus the obverse of this
(CRUCLEAN). parameter is a rough indication as to when the
crude oil will solidify to a sludge form in the
This paper will briefly address some of the cargo tanks.
overall findings from the CRUCOGSA project
under the titles of the three differing phases that Some Statistics for the Database Content
can be found in a crude oil cargo; namely,
Vapour, Liquid and Sludges. Number of diverse types of Samples
Received from differing stages of the
However before doing so it is necessary it is voyages: 2,024
necessary to supply a broad outline of the
physical parameters that are used today in Number of differing Crude Oil types
operational decision making that impact the analysed: 73
efficiency of Crude Oil tanker cargo operations
and the transportation of this material. Number of Vessels taking part of
differing categories: 24
Volatility of Crude Oil
Number of Crude Oil Voyages : 361
Clearly, the volatility parameter will impact both
the efficiency and effectiveness of pumping and In addition to the analytical data to be
discharge of cargo (NPSH criterion) and the obtained from the samples received the
extent of pressure build up in the cargo tanks
Database also records the following
during the voyage. The physical parameter
currently used and available for guidance in information received from the participating
decision making for these consequences in that vessels.
of the cargo’s Reid Vapour Pressure. This
parameter measures the volatility of the crude oil Data Type or Frequency of
as a pressure at a liquid/vapour temperature of Description Reporting
100 degs F (37.8 degs C) with a liquid to vapour Cargo Tanks’ Temp., Daily
ratio of 1:4. Top Middle and Bottom
Sea Water Temperature Daily
Liquid Phase Physical Parameters Air Temperature Every 4 hours
Inert Gas Line Pressure Every 4 hours
The two main parameters mainly referred to are
those of, Density (at 15 degs C) or its equivalent Vessel Rolling/Pitching Every 4 hours
parameters – Relative Density or API Gravity code
recorded at 60 degs F – and, the oil’s Kinematic Vapour pressure release As occurring
Viscosity at a single defined temperature – or Top Up data
typically 40 degs C. These parameters are Wind Speed, Sea State Every 4 hours
important to a vessel for the quantification of its and Vessel Course
cargo and assessing the required cargo
temperature to render the cargo in a pumpable (a) O.B.Q. Report and Slop Tank/s quantities
state. before loading
(b) Vessel’s cargo calculation upon
completion of loading
(c) Vessel’s cargo calculations prior to marked increase in pressure at a Vapour to
discharge Liquid ratio of 0.2:1 (approximately equivalent
(d) Vessel’s R.O.B. report upon completion of to an 80% filled tank) – see figure 1 appended
discharge hereto.
(e) Identification of tanks that are crude oil
washed during discharge Clearly, the extent of pressure to be developed is
dependent upon the concentration of
As will be appreciated, with the foregoing hydrocarbon vapour present in the vapour phase
information a fairly clear overview of the but, notwithstanding this circumstance and by
conditions prevailing onboard the vessels could reference to early findings from the VOCON
be obtained together with manner in which the project currently being undertaken, it would
cargo was behaving from the comparison of the seem that when plotting the total hydrocarbon
diverse analysis results of the cargo’s physical concentration in a vapour phase against a total
parameters. cargo tank filling percent the same inflection
occurs at roughly the same point (see figure 2
A Review of the Findings so Far appended hereto – courtesy VOCON Project).

The Volatility of Crude and its Vapour Phase By reference to a selection of data from the
CRUCOGSA database it is possible to review
The vapour phase in a cargo tank system above a the behaviour of the vapour space of a volatile
crude oil cargo is a very complex mixture of crude oil cargo during a voyage of 45 days. The
diverse gases. The hydrocarbon vapours are, by graph reproduced as figure 3 appended hereto
definition, a potentially Saturated Vapour shows the diurnal pressure fluctuations
mixture whereas, the alternative gas present occurring within the vapour space onboard the
from the Inert Gas supply are Unsaturated gases. vessel and the variations of the cargo
Given these circumstances the differing temperature which in turn determine the extent
vapours/gases will behave in different ways with of the True Vapour pressure of the hydrocarbon
changes in the environment impacting the tank vapours.
vapour phase.
Given that a Saturated Vapour pressure is
However before discussing this issue further it is dependent upon the liquid phase temperature
important to discuss two initial findings that then the diurnal fluctuations in pressure, as can
relate to the volatility parameter currently used be seen from figure 3, must be due to the
to inform on this criterion; namely, the Reid unsaturated gas component (the Inert Gases)
Vapour Pressure. It was noted that by within the vapour phase of the cargo tank system
undertaking a comparison with historical data being heated during the day and behaving in
for crude oils and the analytical findings for this compliance with the Ideal Gas Law.
parameter for the CRUCOGSA load port
samples it would seem that there has been an Figure 3 also records the numerous attempts by
increase in the volatility of crude oils shipped by the vessel’s command to control the tank vapour
sea over the previous 10 to 15 years. pressure with regular manual releases of vapour
Furthermore it was found that, contrary to the to atmosphere. At the present time a vessel’s
expectations for the behaviour of saturated command can determine when it is prudent to
vapours – they should remain isobaric release vapour due to potential over pressure
irrespective of the vapour/liquid ratio or within the cargo tank system they have no
relationship – the Reid Vapour Pressure with its method by which to determine when to stop the
Vapour to Liquid ratio of 4:1 does not reflect the release. Clearly by releasing vapour to a
true vapour pressures to be experienced in a pressure below the true vapour pressure of the
tanker’s cargo vapour system. Plotting cargo at the time (given a cargo temperature)
isotherms for pressure against liquid to vapour will only cause more hydrocarbon vapour to
ratios showed on every occasion, irrespective of evolve from the cargo such that equilibrium is
crude oil type, an inflection occurring creating a restored in the vapour system of the cargo tanks.
To resolve this problem modelling has been integration under the pressure plot could suggest
undertaken using the CRUCOGSA analytical a saving of about 80% of released vapours).
database in order to derive an equation that
could approximate the true vapour pressure to be The Liquid/Sludge Phase
encountered given both the Reid Vapour
Pressure of the cargo and the cargo temperature. The density of a crude oil should be able to give
The model developed simulates the true vapour some indication as to likely behaviour during
pressure that would be experienced in a cargo transportation. After all crude oil types often
tank system filled to 98%. This model is under have the adjective of either Heavy, Light,
refinement such that a third dimension is being Medium etc. which suggests their likely
added; namely, the percent filling of the cargo comparative Density. This can be very
tank system. misleading for the Density is the average
Density and proportion of all the thousands of
The current equation is: compounds within a crude oil. A light crude oil
could suggest that it contains more volatile
(0.0253 * T)
Pt = (1.9181 + (6.2106 * LN(PR))) * EXP component than a medium or heavy crude oil
2.6022 but this is not always the case. It is possible, for
example, to have a crude with a “medium”
Where: Pt is the True Vapour
density but has a “dumbbell” distribution of
pressure (psia) at temperature
T - degrees C compounds with a larger proportion of volatile
PR is The Reid Vapour component, limited or reduced middle fraction
Pressure of the Cargo – psia and then a heavy component content. It is
T is the cargo temperature - therefore that, the analysis programme for the
degrees C CRUCOGSA project included an analysis for
molecular weight distribution by Gel Permeation
Alternatively to the foregoing and by examining Chromatography together with the parameter of
the manner in which the pressure declines during Density.
a controlled release, the True Vapour pressure of
the cargo can quickly be recognised. Figure 4 It should also be stated herein that the form of
appended hereto shows a plot of pressure versus Density for crude oil cargoes is always reported
time during a controlled release of pressure at an international standard temperature of 15
through a vessel’s P/V valve. degrees centigrade. As will be appreciated from
the discussion below relating to the pour point
From figure 4 it can be seen that there are two characteristics of crude oil cargoes, many crude
gradients for pressure decline versus time. The oils exhibit a pour point temperature well above
first part of the release shows a more rapid this standard temperature which in turn requires
decline in pressure and it is this element or that the reported Density is obtained by
partial pressure of the total pressure that is over regression from a measurement at a higher
the saturated vapour pressure (equilibrium temperature within the liquid phase region for
pressure) in the vapour system. The subsequent the crude oil. Problems with regard to the
gradual decline shows the liquid phase trying to accuracy of this form of regression will be
maintain the equilibrium pressure but the rate of discussed below in this paper.
evolution of vapour from the liquid phase is less
than the rate of vapour release from the vapour Before considering the behaviour of Density
system. Thus by monitoring the rate of pressure over the carriage temperature range and the
decline with time the vessel’s command can information that can be deduced therefrom, it is
determine when vapour release should be important to make the correlation between
stopped, namely at the equilibrium pressure. By Density and the other generally referred to
use of such a procedure, it can be seen that a parameter for tanker operations, namely,
large proportion of the currently released Kinematic Viscosity. Taking Dynamic
vapours could be retained onboard tankers (an Viscosity as the basis parameter for flow
resistance characteristics then:
together with the behaviour of these parameters
Dynamic Viscosity (η) = Density (ρ) x at lower temperatures; this behaviour supplies
Kinematic Viscosity (ν) information as to the sludging potential of a
cooling cargo due to the non Newtonian
Thus, Density will vary directly with Kinematic behaviour observed caused by precipitation of a
Viscosity. solidifying phase. Earlier research undertaken
by the author together with confirmation
This circumstance can be seen when figure 5 available from the CRUCOGSA data allowed
(appended hereto) is examined for the behaviour the presentation in 1998 of a “new” parameter
of Bonny Light crude oil over a typical carriage for crude oil to regulatory authorities – the
temperature range. At roughly 18 degrees Cloud Point temperature of Crude Oil.
centigrade the kinematic viscosity increases
rapidly. The reasons for this change in The Cloud Point temperature of a crude oil is the
Kinematic viscosity will be discussed in greater determination of the temperature at the phase
detail below in this paper but is it is due to the boundary between the Newtonian behaviour of
onset of non-Newtonian behaviour of the crude the single liquid phase and the commencement
oil liquid phase. However at the same of Non-Newtonian behaviour for a liquid/sludge
temperature as the Kinematic Viscosity phase. In other words, this temperature predicts
inflection the plot of Density also inflects the commencement of precipitation of sludge
creating a non-linear gradient over the carriage material from the crude oil cargo due to cooling
temperature range. The correlation between of the cargo. Clearly, some, if not all, of this
these two parameters is quite predictable from precipitated sludge phase in suspension within
the standard forms as quoted above but remains the liquid phase could deposit on the floors of a
new knowledge for Maritime crude oil cargo tank increasing cargo loss and presenting a
operations. subsequent pollution threat if not effectively
removed by Crude Oil Washing (COW)
Given that Bonny Light crude oil is not a operations.
volatile type of crude the form of the plot of
density only reveals one inflection over the With this “new” parameter and a decision
temperature range. However, by selecting a making tool for COWing of cargo tanks, a
more volatile crude oil, Arabian Super Light, vessel’s command could:
and reviewing the plot of Density for a similar • firstly predict the potential extent of
temperature range (see Figure 6 appended hereto sludging of the cargo tanks with knowledge
- courtesy CRUMECON Project) a secondary of the extent of sludge forming material in
inflection occurs at the initial boiling point the cargo (normally paraffin waxes as their
temperature for the crude oil – i.e. the evolution basis) and the temperature at which it
of the vapour phase. would start to occur, and
• prepare the necessary wash material to a
Thus, by examining the plot of density over a required temperature to increase the
typical carriage temperature range the phase effectiveness of the COW operation – that
temperature boundaries (Newtonian liquid is remove the sludge from the cargo tanks.
behaviour – single phase) can be obtained for a
crude oil. Due to the profile of the density plot The existing regulations at the time used the
it is clear that difficulties and inaccuracies will parameter of the crude oil’s Pour Point
occur when regressing an observed density at an temperature for this purpose but, as will be
elevated temperature back to the standard readily recognised, this parameter records the
temperature (15 degs C) especially when using completion of this sludging phase; namely, the
the current form of modelling equation – an approach or onset of a total sludge phase which
Exponential curve. commences at the Cloud Point temperature.

Returning to Figure 5 and the correlation A total amendment of Section 9 of the


between Kinematic Viscosity and Density mandatory Crude Oil Washing Manual was
agreed at IMO with the Cloud Point temperature The Analysis of the Pour Point temperature of
replacing the Pour Point temperature of the the many samples received during the
cargo/s as the basis criterion for wash stock CRUCOGSA project revealed another important
preparation for the COWing operation. aspect impacting decision making onboard
However it was necessary to supply a series of tankers. The analysis procedure for the
simple methods for a vessel’s command to necessary Pour Point temperature analysis
calculate this critical temperature. A generalised decided that it was more essential to model the
model to calculate this temperature for the actual circumstances that would impact
normal/mid range type of crude oils was operations onboard a tanker pertaining to this
developed. The final equation needed to use a parameter than by following the prescribed test
commonly reported parameter for the cargo and method for this parameter. The differences
in this regard the cargo’s Pour Point temperature between the two procedures was the methods
was selected. Thus, the equation is: used for the preparation of the sample for
analysis. The prescribed method requires
The Cloud Point temperature: preheating of the sample in order to remove
°C = 20.2 (100.00708x - 0.1157714) + 8 what is termed “the thermal history” of the
sample but in so doing this procedure causes the
volatile solvent fractions to be evaporated from
Where: X is the Pour Point the test sample. What was found by the
temperature in Degrees modified test procedure was that the actual Pour
Centigrade Point temperature for a cargo onboard a vessel
would be significantly lower than that
Alternative techniques are also described within potentially reported on the Certificate of Quality
the revised section but the most accurate method for the cargo. However, for Crude Oil cargoes
for the determination of this parameter is by having higher Pour Point temperatures the
analysis. By undertaking the measurement of 10 difference between the methods used had no
Kinematic Viscosities over a range of discernible difference with the result to be
temperatures that would include the suspected achieved. Thus, from a cargo heating and
Cloud Point temperature, a graph can be pumping perspective the standard Pour Point
constructed of Log Kinematic Viscosity versus Temperature result could be misleading for
temperature. Such a plot can be seen in Figure 7 decision making purposes.
appended hereto.
It was recognised that an important working tool
From figure 7 certain detail can be gained. For that could be supplied to a vessel’s command
example: would be a generalised model for all crude oils
that would predict an envelope of temperatures
• The Cloud Point temperature is that shown for the efficient transportation of a crude oil
by the red vertical line to the “X” axis and cargo. Clearly, the optimum condition of the
not the Blue vertical line. This cargo should be a liquid phase only. This
misinterpretation of the plot can supply a condition can rarely, if ever, occur with respect
very much lower Cloud Point than actual. to a crude oil cargo as a vapour phase (pressure)
• The extent of the angle of inflection supplies will always be present. However, by supplying
an indication as to the likely extent of a minimum/maximum range of temperatures
precipitating waxes. which should maintain the crude oil liquid
• It is to be noted that the plot shows more than volume in a manageable and operationally
one inflection and this records the fact that effective condition should assist in the general
this crude oil contains, as with most crude planning required for the effective transportation
oils, numerous specie of wax each with their and discharge of the cargo.
own “solidification” or precipitation
temperature. The minimum temperature for the designed
model relates to the avoidance of the
precipitation of the sludge phase whereas the
maximum temperature relates to avoidance of intercepts either with the blue or green curves.
excessive vapour pressure necessitating a The green curve represents the Cloud Point or
hydrocarbon enriched release to the atmosphere. lower temperature for a Pour Point obtained
The required input parameters for the model without the pre-treatment process whereas the
have been restricted to those that are potentially blue curve represents the Cloud Point associated
available and recorded on the Certificate of with a Pour Point temperature obtained in
Quality for the specific cargo/es or are contained compliance with the standard testing method
in Annex 1 of the Institute of Petroleum (e.g. I.P. 15). The associated temperatures for
publication “Petroleum Measurement Paper both intercept positions are either 17 or 22 oC
No.8 – Guidelines for Crude Oil Washing of respectively. These temperatures are the lower
Ship’s Tanks and the Heating of Crude Oil being temperature for the final temperature envelope
Transported by Sea”. for which, if the cargo temperature is above the
determined temperature, no sludge deposits
The Parameters are: should be expected.

(a) The Reid Vapour Pressure (p.s.i.a.) – to Before considering the upper temperature and
determine the maximum temperature the associated options available, it is worthwhile
(b) The Pour Point Temperature (oC) – to pointing out the consequences of the loss of the
determine the minimum temperature. solvent or volatile components in the crude oil
with respect to both its Pour Point temperature
Before discussing the model and its function it is and Cloud Point temperature. As can be seen
important to clearly identify the model’s limiting the calculated Cloud Point temperature is lower
functions, i.e. on which occasions and where it with solvents present when compared with the
can be used. These are primarily: situation when some of the solvent is lost during
the heating process thereby causing
1. The temperature guidelines associated with disequilibrium within the crude oil liquid
pressure relate ONLY to a 98% cargo volume phase. If the Cloud Point temperature
loaded condition (further work is being becomes higher as a result of the circumstance
undertaken to further develop this aspect for of heating a crude oil liquid then it follows that
all loading percentages). the Pour Point will also suffer in the same
2. Two variations of Pour Point temperature manner and direction. From an operational
are available subject to the method used to perspective this circumstance is well worth
determine the parameter (reference the noting when considering the behaviour of crude
discussion above relating to the Pour Point oil for pumping of a heated cargo, its
temperature). preparation/heating for use as a crude oil
washing stock, and its saturation of sludges upon
How to use the Model recovery into the slop tanks when used as a wash
medium, amongst many other operational
On the vertical axis of figure 8 of the model circumstances.
inputs can be made for either type of Pour Point
determination (both by the standard method or The maximum value for the temperature
without the pre-treatment of heating – see above envelope is obtained for the temperature of the
for explanation) or the Reid Vapour Pressure. liquid. This temperature will determine when
For the purposes of explaining the use or the required vapour pressure from the model and
operation of this model an artificial crude oil has could be that it requires a vapour release if the
been selected with a Pour Point temperature of - higher pressure requirement is selected. The
3 oC and a Reid Vapour Pressure of 7 psia. model supplies two pressure options with regard
to this criterion; namely, the temperature that
Taking the Pour Point parameter first, and will develop a saturated vapour pressure
following the example shown on the model, an equivalent to 0 mmWG or 1000 mmWG for a
input Pour Point of –3 oC is made. Follow the 98% full cargo volume (the black and red curves
dotted green line horizontally across until it respectively).
project) and liquid behaviour (CRUMECON
Thus, reverting to the example type crude oil project) of crude oils so as to minimise any
with the Reid Vapour Pressure of 7 psia, it can adverse impacts upon the environment due to its
be seen from the model (figure 8) that a transportation and increase the effectiveness of
maximum liquid temperature of either 32 or 35 the transportation process.
o
C will supply the respective saturated vapour
pressures in a 98% full cargo tank system in The effectiveness of tank cleaning in order to
order to achieve a tank pressure of either 0 reduce corrosion and the threat of an unwanted
mmWG or 1000 mmWG in the tank vapour pollutant remains high as a planned research
system. project. With the commencement in the 1980’s
of Crude Oil Washing of cargo tanks to achieve
With regard to the vapour phase and its clean tanks and remove residues, little thought
associated pressures it is worthwhile stating was apparently given to the behaviour of the
again that the observed pressures within the wash medium in this process to gain the
cargo tank system will not be limited to those of effectiveness required. With the data now
the saturated vapour pressure generated by the available from CRUCOGSA a fresh look at this
cargo but will also consist of the variable operation can supply new criteria that would
pressures generated by the unsaturated inert increase the effectiveness of this operation and
gases in the cargo tank vapour system. reduce the unwanted side effects that can occur.
Therefore, dependent upon the extent of use and
presence of inert gas in the cargo tank vapour
system, the vapour pressures will vary over a References:
day with the maximum pressures being achieved
when the inert gas is at its warmest. This
T.J. Gunner – The Physical Behaviour of Crude
variation of unsaturated pressure will not impact
Oil influencing its Carriage by Sea – October
the underlying saturated vapour pressure
1999 – ISBN 82-7860-042-2
generated from the hydrocarbon vapours but will
only add to the total recorded vapour pressure in
the tank vapour system.
Dr. Tim Gunner has a B.Sc. in Maritime
Thus, by attempting to maintain the example Studies and was awarded his Ph.D. by the
crude oil between the temperatures of, say, 22 University of Wales for work done identifying
and 35 oC, a manageable liquid phase will be physical characteristics of crude oils that would
maintained within the cargo tank system. aid in Maritime pollution control. Having been
at sea for 10 years, he has worked as a Marine
and Hydrocarbon Consultant for the last 20
Conclusions years and subsequently being elected as a Full
Member of the London Maritime Arbitrators’
The CRUCOGSA research project has provided Association (now retired). Having recently
a large data source for the behaviour of Crude completed four further years of Fellowship
Oil whilst transported by sea. A start has been research (the CRUCOGSA Programme) he now
made in order to examine, interpret and works as a Technical Consultant to
interpolate the diverse data into working models INTERTANKO undertaking further research
that could assist and guide a Tanker’s command and supplying technical advices to Tanker
in decision making for the diverse operations Owners. He is a Visiting Professor to the
that take place on board such a vessel. Much Maritime Department of Southampton Institute
more work is needed to confirm initial findings and supervises Post-Graduate research.
and develop better tools for those charged with
the responsibility of the transportation of this
important source material by sea.

Current research is currently being undertaken


into both the Vapour behaviour (the VOCON
Appendix - Figures

T o ta l V a p o u r P re s s u re Is o th e rm s
a t d iffe re n t V a p o u r to L iq u id ra tio s

21

19 Ch a m p io n

F o rc a d o s

P a l a n ca
17
B re n t

M a ya
15
O se b e rg
Pressure (psia)

Om an
13 I ra n i a n L i g h t

A ra b i a n S u p e r L i g h t

11 A ra b i a n L i g h t

3
0 0. 1 0.2 0. 3 0.4 0. 5
V a p o r to L i q u i d R a ti o

Figure 1 – Total Vapour Pressure Isotherms for Crude Oils at Different Vapour to Liquid Ratios.
VOC (%) During Loading of
Bonny Light and Brass River Crude Oils

60%

50%

40% Diffusion of Vapour


% Hydrocarbon Vapour

from First Crude Oil


whilst awaiting
commencement of
30% Unsaturated Second Crude Oil Increased
Vapour Vapour
Conditions concentrations
creating
20%
increased
Pressure

10%

0%
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
% Fill of Cargo Tanks

Figure 2. Volatile Organic Compound (VOC %) Measurements Undertaken during the


Loading of a Cargo of Bonny Light and Brass River Crude Oils
Crude Oil Voyage Data for a Volatile Crude oil
Cargo Temperature versus Tank Pressures

30 1600
P/V Valve Opening Pressure

1400
25

1200

20
Temperature Deg C

1000

Pressure mmWG
Tank temp
15 800
Pressure

600
10

Maximium Normal 400


Control Operating
5 Pressure before Manual
Release by Vessel's 200
Command

0 0
0 5 10 15 20 25 30 35 40 45 50
Day Number

Figure 3. Cargo Voyage Data for a Volatile Crude Oil; Cargo Temperature versus Tank Vapour Pressures
V ap o u r relea se o f
Arab Ligh t crud e O il throug h a P /V V alve

1000

900

800

700

600
pressure mmWG

500

400

300

200

100

0
0 5 10 15 20 25 30 35 40 45
T im e (m in u te s )

Figure 4. Graph of Pressure Decline for a Vapour Release for Arab Light Crude Oil through a P/V Valve
D e n s ity R e la tio n s h ip w ith K . V is c o s ity fo r B o n n y L ig h t C ru d e O il
S a m p le N o . 1 0 3 2

0 .8 6 5 500

450

0 .8 6 0
400

350
0 .8 5 5

300

K. Viscosity cst
Density kg/ltr

D e n s ity
0 .8 5 0 250
V is c o s ity c s t

200

0 .8 4 5
150

100
0 .8 4 0

50

0 .8 3 5 0
0 5 10 15 20 25 30 35
T e m p e ra tu re d e g C

Figure 5. A Graph of the Density Relationship with Kinematic Viscosity for Bonny Light Crude Oil
– CRUCOGSA Sample No. 1032
The Behaviour of Density over the Carriage Temperature Range
Arab Super Light
800

795

3 2
y = 0.0005x - 0.0211x - 0.4121x + 791.79
790
Density kg/m3

785

Water Corr. Density


780
Poly. (Water Corr. Density)

775

770

765
0 5 10 15 20 25 30 35
Temperature Deg C

Figure 6. A Graph for the Behaviour of Density over the Carriage Temperature range for Arab Super Light Crude Oil
D aquing C rude Oil
Log K. Visc diagram
sample nos 349 & 351

3.5

2.5
The Size of the Angle
Log K. Visc

of Infle ction
L/P Log Visc
2
D/P Log Visc

1.5

0.5

0
30 35 40 45 50 55 60
Te m pe ra ture de g C

Figure 7. A Graph of Log Kinematic Crude Oil Deriving the Cloud Point Temperature for
Daqing Crude Oil – CRUCOGSA Samples Nos 349 & 351
A n O p tim u m T e m p e r a t u r e M o d e l
f o r t h e T r a n s p o r ta tio n o f C r u d e O il b y S e a

25

20

15
Pour Point (deg C) or RVP (psia)

10

5 R V P p s ia f o r 1 0 0 0 m m W G
R V P p s ia f o r 0 m m W G
C lo u d P o in t T e m p D e g C
0 N e w C ld . P t . T e m p D e g C
10 20 30 40 50 60 70

-5

-1 0

-1 5

-2 0
T e m p e r a tu r e D e g C

Figure 8. An Optimum Temperature Model for the Transportation of Crude Oil by Sea