INTRODUCTION

What is Sulfur Gases?

Sulphur dioxide - If sulphur is present in a fuel, sulphur dioxide is made when it burns.  Sulphur
dioxide, a poisonous gas, causes acid rain and can trigger asthma. Sulphur is often removed from
fuels before they are burned so that pollution is reduced.
Sulfur dioxide is the product of the burning of sulfur or of burning materials that contain sulfur:
S + O2 → SO2, ΔH = −297 kJ/mol
.

Sulfur dioxide can bind to metal ions as a ligand to form metal sulfur dioxide complexes,
typically where the transition metal is in oxidation state 0 or +1. Many different bonding modes
(geometries) are recognized, but in most cases, the ligand is monodentate, attached to the metal
through sulfur, which can be either planar or pyramidal η1.

Sulfur can also be removed from fuels before burning, preventing formation of SO2 when the
fuel is burnt. The Claus process is used in refineries to produce sulfur as a byproduct.
The Stretford process has also been used to remove sulfur from fuel. Redox processes using iron
oxides can also be used, for example, Lo-Cat or Sulferox.
Fuel additives such as calcium additives and magnesium carboxylate may be used in marine
engines to lower the emission of sulfur dioxide gases into the atmosphere.[39]

Combustion of Fuel Oil

One of the most easily available energy sources to power engines on ships is the fuel oil. When
fuel oil is burnt in air, heat is released. This heat can be used to drive internal combustion
engines or to heat up water in boilers to form steam. The process of burning fuel in air is called
combustion. The release of this heat energy can be slow or can be extremely rapid.

Fuel oil at normal room temperature is viscous and not easily ignited. The fuel oil, also called
Bunker C oil, must be heated to around 98 degree Celsius or more before it can be used for
combustion. The Bunker C oil also contains solid particles that can choke up the fine nozzles of
the burner equipment. These are removed by passing through a series of removal methods like
settling, filtering and finally purification.

On ships, when fuel oil is sprayed as a fine mist or atomized in the boiler burners, it is able to
burn at a relatively slow rate as a burning flame.

When fuel is sprayed into the cylinders of diesel engines, the fuel burn in such a rapid rate that
explosions occur. Fortunately, these explosions are internally within the space of the cylinder
liner, piston crown and the cylinder head, protected from persons outside. These engines are
called internal combustion engines.

However fast or slow the combustion rate, it is still a chemical reaction between carbon,
hydrogen, sulfur and oxygen that releases heat. Fuel oil is basically a hydrocarbon that contains
carbon and hydrogen atoms. The reaction when fuel oil is burnt in air can be written as follows:

C + O2 = CO2
2CO + O2 = 2CO
2H2 + O2 = 2H2O

Fuel oil tends to contain sulfur as an impurity. The reaction between sulfur and oxygen is shown
below. The water formed in the above reaction also reacts with the sulphur products as follows:

S + O2 = SO2
2S + 3O2 = 2SO3
SO3 + H2O = H2SO4
SO2 + H2O = H2SO3

The by-products of the combustion of sulphur with air are sulphuric acid and sulphurous acid.
These are corrosive to the equipment and the surfaces inside the engine, the boiler furnace, or the
exhaust trunking. However, sulphur corrosion, also called low temperature corrosion, can be
minimized by maintaining the exhaust temperature above 120 degree Celsius, i.e. above the dew
point when the water in the exhaust gas is able to condense back to liquid.

How is it emitted from burning carbon?

Elemental sulfur is often produced by sour gas wells, primarily due to the oxidation of hydrogen
sulfide. This may occur as a result of oxygen contamination. Alternatively, with pressure and
temperature changes in the line, sulfur may precipitate and deposit on the pipeline walls. In the
presence of water, contact of solid sulfur with mild steel can result in the onset of catastrophic
corrosion processes as shown on figure below.

The objective of this Report is to study the effect of elemental sulfur on the corrosion of mild
steel. In preliminary experiments, elemental sulfur hydrolysis and sulfur-mild steel corrosion
were investigated asa per figure below.
Sulfur was found to react with water at temperatures of greater than 80o C, resulting in
significant acidification of the corrosion solution. It was also found that elemental sulfur can
cause localized corrosion of mild steel when they are in direct contact.
Iron sulfide films/scales readily formed on the surface of the steel; these were analyzed by
infinite focus microscopy (IFM), scanning electron microscopy (SEM) and X-ray diffraction
(XRD).
Sulfide stress cracking is a form of hydrogen embrittlement which is a cathodic cracking
mechanism as per figure below.
It should not be confused with the term stress corrosion cracking which is an anodic cracking
mechanism. Susceptible alloys, especially steels, react with hydrogen sulfide, forming metal
sulfides and atomic hydrogen as corrosion byproducts.
Atomic hydrogen either combines to form H2 at the metal surface or diffuses into the metal
matrixes per figure below.
 Since sulfur is a hydrogen recombination poison, the amount of atomic hydrogen which
recombines to form H2 on the surface is greatly reduced, thereby increasing the amount of
diffusion of atomic hydrogen into the metal matrix. This aspect is what makes wet H2S
environments so severe.
Since SSC is a form of hydrogen embrittlement, it is most susceptibile to cracking at or slightly
below ambient temperature.
Sulfide stress cracking has special importance in the gas and oil industry, as the materials being
processed there (natural gas and crude oil) often contain considerable amounts of hydrogen
sulfide.
Equipment that comes in contact with H2S environments can be rated for sour service with
adherence to NACE MR0175/ISO 15156 for oil and gas production environments or NACE
MR0103/ISO17945 for oil and gas refining environments.
"High Temperature Hydrogen Attack" does not rely on atomic hydrogen. At high temperature
and high hydrogen partial pressure, hydrogen can diffuse into carbon steel alloys. In susceptible
alloys, the hydrogen combines with carbon within the alloy and forms methane. The methane
molecules create a pressure buildup in the metal lattice voids, which leads to embrittlement and
even cracking of the metal.Sulfidic corrosion, also known as sulfidation, is the term used for high
temperature corrosion (above 450F / above approx. 260°C) of steel in contact with sulfur (Fe
reacts with S to form FeS)
Experimental Procedures
Elemental sulfur can readily form in aqueous systems via the oxidation of sulfide species.
1- Possible reactions for the formation of elemental sulfur (S8) could involve high
oxidation state metals (denoted Mn+) or oxygen: 8 H2S (aq) + 16 Mn+ (aq) → S8 (s) +
16 H+ (aq) + 16 M(n−1)+ (aq) (1) 8 H2S (aq) + 4 O2 (g) → S8 (s) + 8 H2O (l) (2).
In addition to strictly chemical processes, sulfide oxidizing bacteria have been shown to
form liquid sulfur droplets under ambient conditions.
2- Consequently, the formation of elemental sulfur is almost inevitable in H2S corrosion
environments in the field. Elemental sulfur is shown as S8 in the reaction equations
below as that represents the stable allotrope of sulfur under standard conditions.
Acidification in sulfur containing aqueous systems has been reported, with species such
as H2S, H2SO2, H2SO3, H2SO4 and polysulfides being possible candidates as
hydrolysis products.
3- MaldonadoZagal and Boden4 proposed that acid formation as a result of sulfur hydrolysis
was the main factor governing corrosion in the presence of elemental sulfur: S8 (s) + 8
H2O (l) → 6 H2S (aq) + 2 H2SO4 (aq) (3) Alternatively, MacDonald et al. hypothesized
that an electrochemical reaction between iron and polysulfide is the driving force for
corrosion in systems where elemental sulfur is present.5,6 (x-1)Fe + Sy-1⋅S2− + 2 H+ →
(x-1)FeS + H2S + Sy-x (4)
The objective of this Report is to study the effect of elemental sulfur on the corrosion of
mild steel, with particular emphasis on detection of pH effects, identification of formed
corrosion products, study of pitting phenomena and measurement of general/localized
corrosion rates. EXPERIMENTAL PROCEDURE Experiments were conducted to
determine temperature effects on the acidification of pure water with elemental sulfur.
This involved adding elemental sulfur to deoxygenated deionized water purged with
nitrogen and measuring the pH of each test system with time. The chosen temperature
range was 25-150°C. Experiments were conducted in both glass cells and autoclaves. For
the corrosion experiments, elemental sulfur (ACROS 99.999%) was deposited onto
polished coupons by heating it slightly above its melting-point (115°C) then pouring it
onto the coupon surface (C1018 steel). This gave uniform coverage of adherent sulfur to
the coupon surface. Care was taken not to oxidize the sulfur as it was heated. Coupons
thus prepared were then transferred to a glass cell for corrosion experiments.
Conditions for the elemental sulfur corrosion experiments are summarized in the test
matrix outlined in Table 1.
 Corrosion coupons were removed from the glass cell and characterized after 1, 4 and 5
days. Prior to analysis, unreacted sulfur was mechanically removed from the coupon
surface.
Samples were characterized with a JEOL6390LV scanning electron microscope (SEM),
EDAX energy dispersive Xray fluorescence attachment (EDX), Alicona infinite focus
microscope (IFM) and Rigaku Geigerflex Xray diffractometer (XRD); XRD data was
taken from films directly on the corrosion coupons.
Corrosion products were then removed by treatment with Clarke solution, ASTM
standard G1 section 7.7.2 approved by ASTM committee April 24 1981, and the
corrosion coupons re-characterized by IFM. Localized corrosion rates were determined
by analysis of IFM data whereas general corrosion rates were obtained by weight loss
methods.
2 RESULTS Acidification of water with elemental sulfur Significant acidification of
water upon exposure to elemental sulfur was measurable only at temperatures in excess
of 80°C, as shown in Figure 1.
The pH values shown there were obtained after waiting for at least a few hours while the
measured pH stabilized. The results confirmed that hydrolysis products were indeed
being formed by reaction of elemental sulfur with water, be they H2S, H2SO2, H2SO3,
H2SO4 and/or polysulfide species. The pH values measured were significantly higher
than those reported in a similar study by Maldonado-Zagal and Boden4 , however it is
difficult to establish why.
Also, it is not clear if this mechanism can be used as an explanation for localized attack
on mild steel by elemental sulfur, as the lowest pH values observed fall within the typical
range of pH seen in water/CO2 systems. Elemental sulfur corrosion experiments a
coupon with elemental sulfur on the surface prior to exposure is shown in Figure 2.
The portion of the coupon surface which was in direct contact with the elemental sulfur
was significantly blackened after exposure; this was due to the formation of iron sulfide.
A typical coupon surface, after the reaction, is shown in Figure 3.

Representative SEM/EDX data for the corrosion coupon surface that has been in direct
contact with elemental sulfur for one day at 25°C is shown in Figure 4.
Note that most of the surface film resembles a blistered layer (top left SEM image).
Cracking of the film shown in the enlarged image, reveals that it is very thin, which
seems to be exfoliating from the surface. A further enlargement of the small area shows
that the film appears amorphous, with no well defined morphologies present; this was
confirmed by XRD. The composition of the film was shown to consist of iron sulfide by
using EDX. The IFM image of the corrosion coupon after the iron sulfide has been
removed reveals some pitting corrosion, Figure 5.
The top right image corresponds to the small region marked on the “whole coupon”
picture to the left of it. The line across the “twin pits” corresponds to the profile data at
the bottom of the figure. Note that the first pit has a depth of ca. 18 µm whereas the
second pit is ca. 12 µm. Comparison of general and localized corrosion rate data of
generated samples is given below. After four days at 25°C a thicker film has formed at
the surface, see Figure 6.
The exfoliation of the film is obvious on the enlarged image on the top right. The origin
of the lines on the underside of the exfoliated film are due to the polishing marks on the
original steel substrate, which have left an imprint on the sulfide film formed by a solid
state reaction. Cracking of the film is more severe on this coupon than the one exposed
for only one day. From EDX and XRD, it is clear that the film chemistry remains
fundamentally unchanged in the longer exposure. Film pit depths appear similar to those
observed after 1 day; however, the profile shown in Figure 7 seems to indicate a
broadening effect.
After a 5 day exposure at 25°C, see Figure 8, the films seem to be even thicker and
coarser than before, but pit depth remains similar, see Figure 9. Another similar series of
experiments was conducted at 80°C.
After one day at 80°C there is a much thicker film present on the coupon surface than
was observed at 25°C, see Figure 10.

Distinct iron sulfide microcrystallites seem to have formed. The pitting depth is again
about 15 µm, see Figure 11. After 4 days at 80°C, Figure 12, the film has become thicker
and coarser, appearing more crystalline.
Pitting depth remains at ca. 15 µm, Figure 13, but broadening is again observed. Pit
density on the surface also appears to be increasing. After 5 days at 80°C, Figure 14, the
entire surface seems to be covered by a coarse and cracked film.

From XRD, the dominant phase is the crystalline iron sulfide 3 mackinawite, see Figure
15.
Mackinawite is a layered structure which is common in aqueous environments under
mildly sour conditions.
7 Comparison of general and localized corrosion rates are shown in Figures 16 and 17.

Both refer to the steel surface area underneath the elemental sulfur deposit. At 25°C, the
localized corrosion rate (pitting) decreased from 7.2 mm/yr after one day to 1.7 mm/yr
after 5 days.
The general corrosion rate remained essentially unchanged at ca. 0.80 mm/yr. At 80°C,
the localized corrosion rate was 5.1 mm/yr after one day, but was reduced to 3.0 mm/yr
after 5 days. The general corrosion rate was 1.6 mm/yr at 80°C, double the general
corrosion rate measured at 25°C. It is worth noting that the thick deposits of iron sulfide
on the steel substrate formed directly beneath the elemental sulfur.
Consequently, a direct solid-state reaction for the formation of iron sulfide from
elemental precursors is a more likely process which may occur in these systems: 8 Fe (s.)
 + S8 (s.) → 8 FeS (s.) (5) Such a reaction path does not depend on the generation of
acidic species when water is exposed to elemental sulfur.

CONCLUSION
Significant acidification of water by its reaction with sulfur did not occur at temperatures
lower than 80°C. This mechanism is thought to be less significant than the direct reaction
of elemental sulfur with the steel surface. • Corrosion product films generated by the
direct reaction of elemental sulfur with C1018 steel were confirmed to be iron sulfide.
Corrosion films became progressively thicker with time.
Little change was observed in general corrosion rate with time. Pitting rates were
significantly higher than the general corrosion rates.

REFERENCE
1‐ https://en.wikipedia.org/wiki/Sulfur_dioxide 
2‐ http://www.bbc.co.uk/education/guides/z6xbkqt/revision/3 
3‐ http://www.ourladys.n‐
lanark.sch.uk/OLHSDepartments/OLHSscience/chemistrynotes/Burning%20Hydrocarbons‐
Pollution.pdf 
4‐ http://www.free‐marine.com/i3combustion.htm 
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6‐ https://www.ohio.edu/engineering/corrosion/research/upload/8172‐20.pdf 
7‐ https://en.wikipedia.org/wiki/Sulfide_stress_cracking 
8‐ http://www.csiheat.com/Uploads/files/Preventing%20Corrosion%20in%20Sulfur%20Storage%2
0Tanks.pdf 
9‐ http://www.brighthubengineering.com/power‐plants/46351‐cold‐end‐corrosion‐in‐a‐boiler‐
and‐its‐prevention/