Effective Assessment of Crude Oil Sourness for the Material

Selection of Refinery Feeder Pipeline

Javad Khosravi, NIORDC/NIOEC, Tehran/Iran; javad khosravi

Summary

Doubtless, in the oil and gas industries, H2S presence is the main cause for
so-called sour services corrosion. NACE standard MR 0175/ISO 15156
provides the guideline to determine the degree of sourness of gas, liquid or
multi-phases services and the material required. The sour service aspects
may differ from a process engineer to a material engineer and it is sometimes
due to the different concepts about dissolved H2S concentration. The worst
possible operating conditions include maximum temperature and H2S partial
pressure in the gas phase and crude oil composition usually use for
evaluation of the sourness level. The present work comprises the
investigations carried out on crude oil and provides the results obtained from
the analysis of major parameters influencing the crude oil sourness. It should
be noted that although the mentioned crude oil is fed into an oil refinery but
the present study has its focus on material selection of a transportation
pipeline and the relevant facilities.

1 Introduction

Crude oil quality can be evaluated by the terms of density (light to heavy)
and sulphur content (sweet to sour). In accordance to American Petroleum
Institute (API), the crude oil density should be measured at a temperature of
60 ºF [1]. The higher the API gravity [2] means the lighter the crude oil. Light
crude oils have commonly the API gravity above 38 degrees while the heavy
crude an API gravity of 22 degrees or less.

In the oil and gas industries, the terms sour and sweet are referred to the
sulphur content of crude oil or gas. Oil classification by the sweet and sour is
the best way to define what the crude oil really is. By the processing point of
view, sweet crude implies that the refinery costs are lower since most
refineries to begin with are only processing the sweeter crude products. On
the other hand, this type of crude has fewer impurities as compared to the
other and is a lot easier to process.

It is agreed that due to the sulfur content, the crude oils are categorized into
three different groups. The first is low sulfur crude oil, the second is termed as
intermediate crude oil and the last one is the high sulfur crude. The first one
refers to the sweet crude contains less than 0.5% sulphur (by weight or
5000ppm); the second category has a sulfur value ranging from 0.5% to 1%.
Whereas the high sulfur crude oil (sour crude) has more than 1% sulfur. It
should be noted that the fewer the sulfur in the oil make it more friend to the
environment and it is also easier to refine with the lower costs.

It should be noted that the most sulphur in crude oil is actually bonded to
carbon atoms as organic compound e.g. “mercaptan” with the chemical
formula CH3SH; however, high quantities of hydrogen sulphide (H2S) in sour
crude can pose serious health and corrosion problems. Below table shows a
brief comparison of hydrogen sulphide properties to methyl mercaptan. [3]

Table 1: Some properties of hydrogen sulphide and methyl mercaptan

Solubility in
Physical state at Boiling point Vapour specific
Substance water (20° C)
1 atm and 15° C (° C) gravity
(TLV)

Hydrogen
Gas -60.33 1.2 4.1 gram/lit
sulphide

Methyl
Gas 6.2 1.66 -
mercaptan

Hydrogen sulphide (H2S) is a heavier than air, colourless gas with a sweetish
taste and characteristic odour of rotten eggs. Hydrogen sulphide is slightly
soluble in water and acts as a weak acid. This weak acid can be dissociated
as bellow:

H2S  H+ + HS- pKa1 = 7.04

HS-  H+ + S2- pKa2 = 11.96

There are many reports about the sudden failures of steel pipeline associated
with their exposure to H2S containing fluids. Sulphide stress cracking (SCC)
can occur when H2S in crude oil is in contact with carbon steel pipeline
(especially high strength steels). SCC is an embrittlement phenomenon in
which failures can occur at stresses below the yield strength of the metal [4].
For a susceptible steels, SSC may occur when two conditions are met, a
tensile stress which can be residual/ applied and presence of hydrogen
sulphide. SSC begins when steels and other susceptible alloys form a
reaction with hydrogen sulfide, resulting in atomic hydrogen and metal
sulfides as byproducts of corrosion. In turn, atomic hydrogen can diffuse
through metal surface and disperse into the matrix of the metal. Now the
metal is suspected to brittleness and can be subjected to cracking through
any stress. Sometimes two atoms of hydrogen can recombine again in the
metal bulk where there is sufficient space for a hydrogen molecule (H2) to be
trapped. In this case, commonly in the place of inclusion or any elongated
impurities (e.g. manganese sulphide), cracking/lamination by induced
hydrogen is expectable (HIC).
Some ions such as sulfur, cyanide and ammonium acts as a hydrogen
recombination preventer. They increase the levels of atomic hydrogen on the
surface of steel and therefore increasing the atomic hydrogen diffusion. Since
the sulphur presence in water phase is the main cause for what called SSC or
stress corrosion cracking, the light crude oils cause less damage to refineries,
transportation pipeline and the relevant facilities resulting to the lower
maintenance costs over time. For example, the presence of wet hydrogen
sulphide in crude oil transportation pipeline can create significant metal
degradation in the form of brittleness, lamination and cracking.

2 Sour crude oil pipeline and material selection

For a long crude oil transportation pipeline, an accurate assessment of the

degree of sourness is very important because taking the sour services
considerations including NACE material and construction concerns may
impose big costs to the project. Metallurgically, it is accepted that high
strength steels are more suspected to brittleness and sour oil services failures
[5]. On the other hand, depending to the sour service pipeline total pressure,
higher wall thickness is needed when using a lower strength steel. As
mentioned before, sour crude oil is commonly defined as oil with a sulphur
content of above than 0.5%. This is however a processing concept and can’t
satisfy the material selection requirements. As stated by NACE MR0175/ISO
15156 [6], the severity of the sour environment, with respect to SSC of a
carbon or low alloy steel can be assessed using bellow figure:

Figure 1: SSC regions for material selection

As seen above, for the gas free crude oils, in situ pH and H2S partial pressure
are required to determine the sour service region. Different regions need to
the different considerations as detailed by the mentioned standard. Acidic
environment (or lower pH) means the higher number of hydrogen ions [7] and
the higher H2S partial pressure means the more likelihood of sulphide ions
(Hydrogen recombination preventer) presence in the water phase. In situ pH
can be measured by a suitable method (e.g. the method explained by annex
D of NACE MR0175/ISO 15156 and EFC publication 17). The partial pressure
of H2S can also be calculated by bellow equation:

%
H2S partial pressure (kPa) =

The crude oils include some natural gas in solution. The pressure at which
this natural gas begins to come out of solution and form bubbles is known as
the bubble point pressure. As seen by above equation, there is a directly
proportional relation between the bubble point pressure and H2S partial
pressure. On the other hand, the bubble point is depended to crude oil vapour
pressure that means it is a function of service temperature. The bubble point
should be determined at operating temperature, as quoted by NACE
MR0175/ISO 15156.

There is also a directly proportional relation between the H2S partial pressure
and H2S mole fraction in gas phase. With respect to the H2S boiling point; -
60.33 °C given in table 1, for a crude oil transportation pipeline in its normal
operation conditions, H2S is dissolved as a gas in liquid hydrocarbon. Based
on Hennery law, the solubility of hydrogen sulphide in a liquid crude oil is
directly proportional to the partial pressure of the gas above the crude oil and
reverse proportional to the crude oil temperature. In other word, depending
crude oil composition, any change in the temperature can cause to the higher
amount (mole fraction) of H2S in the gas phase.

It should also be noted that the crude oil contains a variety of hydrocarbon
components of different molecular weights and boiling temperatures. As crude
oil temperature increase the lower molecular weight components start to
evaporate and can change the H2S mole fraction in gas phase. It means,
depending to crude oil composition, when temperature increases, some
dissolved gases will escape by their bubble point while some light
hydrocarbons will evaporate through their low boiling points.

3 Worst conditions simulation

When a long pipeline is used for transportation of sour/sweet crude oil from an
upstream delivery point to the oil refinery, it is important that the worst
possible conditions are considered for its material selection. As explained
before, the bubble point pressure and mole fraction of H2S in gas phase may
influence by multiple parameters, hence they may be difficult to determine by
the general calculation methods. Nowadays, there are many reliable soft-
wares which make the chemical process simulation easy. Amongst them
“Aspen HYSIS” is a well-known and comprehensive process modelling
system which is recommended by the most of process engineers. The primary
data inserted to the software are very important and they should be based on
the worst possible conditions [8].

4 Using crude oil assay for the sourness evolution- A case study

As an example, Figure 2 shows the data fed to the Aspen HYSIS software.

Figure 2: Data obtained from crude assay are fed to simulation software

These data are a portion of the results obtained from laboratory assay of a
crude oil (24 ppm of H2S content) which to be transported via a long pipeline
from a delivery point to the oil refinery. In-situ acidity calculation shows a pH
of 4.8.
For a long buried pipeline, operating temperature may vary by the stream
temperature and also may influence by the soil temperature. Pipelines are
installed at ambient sea water temperature of say between 4° C and 10° C
while the temperature of buried pipelines, even when are surrounded by the
warm soil, can never rise above 35°C. Figure 3(a, b) show the bubble point
pressure and H2S mole fraction at 20°C.

Figure 3(a): The simulation result shows that bubble point pressure is 24.30 kPa at 20 °C
 Figure 3(b): The simulation results show the H2S mole fraction as 0.013991 at 20 °C

For the mentioned crude oil, the H2S partial pressure is therefore 0.3399 kPa
at 20 °C. Some crude pipeline records show the temperature of 5 °C to 35 °C
(in some cases 40°C) as actual operating temperature. Maintaining the actual
conditions, simulation has therefore been carried out at these possible
temperatures (say 5, 10, 15, 25, 30, 35°C). The results are given by table 2.

Table 2: The relation between temperature and H2S partial pressure

Bubble point H2S mole H2S partial
No Temperature(°C)
pressure(kPa) fraction pressure (Kpa)
1 5 15.79 0.016241 0.2564454
2 10 18.30 0.015434 0.2824422
3 15 21.14 0.014697 0.3106945
4 20 24.30 0.013991 0.3399813
5 25 27.83 0.013320 0.3679126
6 30 31.75 0.012684 0.4027170
7 35 36.09 0.012080 0.4359672

As seen above, the operating temperature and bubble point pressure are
directly proportional whereas the H2S mole fraction is inversely proportional to
temperatures. It can be attributed to the evaporation of the light components
of crude oil with temperature increasing. One the other hand, the partial
pressure shows a non-exact linear behaviour with temperature increasing. For
clarity, the results at 10°C and 30°C are marked in the NACE MR0175/ISO
15156 material selection plot. (Figure 4)

Figure 4: A change in operating temperature may change the material region

5 Conclusions

1. Process engineers and corrosion engineers may have two different

concepts about the sour services, first by the total ppm of sulphur in
crude oil and the second by the maximum H2S can immigrate from the
hydrocarbon phase to aqueous phase under specified circumstances.

2. The crude oil contains a variety of components and their complexity

can make the calculation difficult. Computation by reliable simulating
software is therefore recommended for the critical parameters.

3. Simulation is recommended to be carried out for the all possible

operating temperatures. Actual temperature records in similar
conditions are preferred.

4. It should be noted that depending to the crude oil chemical

composition, a small change in temperature may vary the material
region.

5. Improving the pipeline integrity, the worst possible temperature should

be considered for the pipeline material selection.

6 References

[1] ASTM D 1250 (2008), “Standard Guide for Use of the Petroleum Measurement
Tables”, (West Conshohocken, PA: ASTM), 2008.

[2] ASTM D 287 (2000), “Standard Test Method for API Gravity of crude petroleum and
petroleum products (Hydrometer Method)”, (West Conshohocken, PA: ASTM), 2000.

[3] P. G. T. Fogg and C. L. Young, Eds., “IUPAC Solubility Data Series”, Vol. 32,
Hydrogen Sulphide, Deuterium Sulphide, and Hydrogen Selenide, Pergamon Press,
Oxford, England, 1988.

[4] ASM HDBK VOL 11 (2002) “Failure in sour gas environment”, American society of
material, ASM International, 2002.

[5] API Specification 5L/ISO 3183 (2007), “Petroleum and natural gas industries-Steel
pipe for pipeline transportation systems”, American Petroleum Institute, 1220 L Street.
N.W. Washington, D.C. 20005, 2007.

[6] NACE MR 0175/ISO 15156-2 (2003), “Petroleum and natural gas industries -
Materials for use in H2S-containing environments in oil and gas production" (Houston,
TX: NACE), 2003.

[7] BONIS M. and CROLET J-L., “Practical aspects of the influence of in situ pH on H2S-
induced cracking” , Corrosion Science, 27, pp. 1059-70, 1987.

[8] R. P. Hesketh and M. J. Savelski., “Introduction to HYSYS Simulation Bubble Point,

Dew Point and Flash Calculations”,Chemical Engineering, Rowan University, 2002.