Sulfur Storage Pits in Petrochemical Plants: Deterioration

Mechanism, Materials Selection, and Repair

Zakaria S. Alhelal1
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.

Abstract: To mitigate concrete sulfur storage pits deterioration, it is important to understand the mechanisms leading to concrete deterioration.
The Claus chemical process is the industry standard for obtaining sulfur from hydrogen sulphide gas (derived from natural gas). The deterio-
ration of concrete pits can be from both environmental factors and chemical effects of the Claus process. This may take the form of corrosion,
sulfation, acidic attack, thermal expansion, or polymerization. Corrosion occurs as a result of sulfuric acid formation. Reactions occur because
of Claus products presence, ingress of water through the concrete matrix or from leaks in steam coils. Sulfation occurs mainly from catalyzing
some of Claus products by concrete or its admixtures. An acid environment lowers the pH value of the concrete and leads to impacting the
passive film protecting the reinforcing rebars. Effects of thermal expansion and polymerization are also discussed in this paper. Selection of
the proper materials is crucial in the construction of a durable sulfur pit. Low porosity concrete prevents ingress of gas/liquid species inside
the concrete and hence mitigates destructive chemical reactions inside the structure. Cementious materials that will lower the diffusion of
gas and liquid such as silica will improve the durability of the sulfur pits. In addition, because of the pozzolanic reaction associated with
the use of silica fume the Ca(OH) content will be reduced. Concrete with mineral additives such as silica fume will result in higher compressive
strength, lesser permeability and higher corrosion and sulfate resistance. To assure the structure durability, designers need to understand and
envision the operational conditions of sulfur pits. Utilization of wrong materials and construction practices can significantly shorten the
expected service life of sulfur pits. Finally, repair of deteriorated sulfur pits needs also to be evaluated and conducted by specialized personnel.
This repair can take many forms and scenarios including crack repair, structural members repair, durability liner, and structural liner. A proper
strategized and engineered repair should be implemented to ensure the repair’s effectiveness and durability. DOI: 10.1061/(ASCE)SC.1943-
5576.0000165. © 2014 American Society of Civil Engineers.
Author keywords: Sulfur; Pit; Sulfation; Deterioration; Repair; Durability; Corrosion; Hydrogen sulfide; Claus; Sulfuric.

Introduction
Sulfur, denoted with the symbol S, is the chemical element that has the
atomic number 16. Elemental sulfur is extracted from hydrogen sul-
fide existing in natural gas or produced in hydrodesulfurization of
petroleum. The Claus process is the industry standard for sulfur ex-
traction. Typically sweet crudes have #0:05% sulfur content, while
sour crudes have $1:5%. Once extracted to molten form, the sulfur is
stored in a variety of different type of vessels. These vessels can be
carbon or stainless steel, aluminum-alloy or RC, which are generally
below-grade concrete pits. This is usually required because of gravity
process–flow considerations. Sulfur pits require steam heaters to
maintain sulfur in liquid phase. Pits can be classified as working
pits, with fluctuating levels of sulfur, or storage pits.
Attack and Deterioration Mechanisms
Sulfur concrete pits deteriorate from chemical and environmental
factors. The deterioration can be from numerous mechanisms. The
chemical factors, related to the Claus process, include sulfur-forming
1 ceptable and safe level. This causes oxidation inside the pit as H2 S
Civil Engineer, Saudi Arabian Oil Company, P.O. Box 5000, Dhahran
31311, Saudi Arabia. E-mail: alhelazs@aramco.com
Note. This manuscript was submitted on December 21, 2010; approved
on January 31, 2013; published online on September 26, 2013. Discussion
period open until July 11, 2014; separate discussions must be submitted for
individual papers. This paper is part of the Practice Periodical on Struc-
tural Design and Construction, © ASCE, ISSN 1084-0680/04014005(6)/
$25.00.
reactions and corrosion from the presence of liquid sulfur, H2 O, SO2 ,
and O2 (Fig. 1). If the structure gets penetrated by groundwater or
process condensate (e.g., from leaking steam traps), then it reacts with
molten sulfur and forms sulfurous acids. It is the same situation when
steam coils inside the pit leak. During work experience in sulfur plants
unit at the Shedgum Gas Plant, Saudi Arabia, this led to major repairs
during regular units’ testing and inspection. Such leaks in some
situations led to a unit shutdown. In an aggressive sulfur pit en-
vironment, it is generally required to have concrete resistance
toward chemical reactions, metal corrosion, and swings in
temperature.
Corrosion
The corrosion can occur through formation of sulfuric acid in the
system. Liquid sulfur contains dissolved H2 O, O2 , SO2 , and other
components that are present in the process gas. H2 S is also present
both as dissolved species, in the liquid sulfur, and also in chemical
combination with sulfur
H2 S þ S8 → H2 Sx
The air exists in the process to lower H2 S concentration to an ac-
and H2 Sx oxidize and form H2 O (Fig. 2)
H2 S þ 1=2 O2 → 1=8 S8 þ H2 O
Formation of SO2 also occurs through oxidation of the sulfur under
conditions leading to deep degassing of the sulfur. These conditions
result in formation of sulfuric acid under the presence of water.

© ASCE 04014005-1 Pract. Period. Struct. Des. Constr.

Pract. Period. Struct. Des. Constr. 2014.19.

 Sulfuric acid attacks on metals and alloys result in corrosion of
both carbon and stainless steels. Ingress of water, on the other hand,
and its contact with embedded steel results in corrosion products.
This exerts tensile stresses on concrete and causes failure in the
protective concrete cover (concrete surface spalling).
Reinforcement steel bars located above molten sulfur levels,
within the vapor zone, can corrode because of the electrochemical
process in the presence of oxygen and moisture. Steel bars below the
vapor zone can lose the critical bond required for composite action
of the structural cross-section. The liquid sulfur-air interface is the
most damaged area. This can be identified easily during regular
testing and inspections. A portion of the pit wall may be bricked in
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.
that region to protect concrete from deterioration. The bricks should
be capable to sustain the pit’s aggressive environment.
Sulfation
In the head space region of the holding structure, all gas phase species
may penetrate the concrete because of its porosity and this includes
sulfur vapor, H2 S, SO2 , and O2 . O2 could be involved in direct oxida-
tion of H2 S to sulfur, resulting in sulfur formation inside the structure.
Also H2 S and SO2 can be catalyzed within the holding structure
by CaO to form sulfur and water (Fig. 3). SO2 and O2 are adsorbed
by CaO surfaces and react slowly to form calcium sulfate CaSO4 .
High silica concretes, the preferred materials for sulfur concrete
pit construction, also contain trace amounts of CaO, Na2 O, MgO,
and many other materials that can catalyze sulfur formation within
the holding structure
Fig. 1. Interior of holding structure (Clark, Dowling and Bernard 2009,
with permission from ASRL)
Fig. 2. T.O. sucks and burns gases from the pit (Clark, Dowling and Bernard 2009, with permission from ASRL)
© ASCE
Pract. Period. Struct. Des. Constr. 2014.19.
2 H2 S þ SO2 → 3=8 S8 þ 2 H2 O
Sulfur formed within the structure could be in liquid or solid form
depending on the depth of its penetration. Solidification of the sulfur
is driven into the wall by the thermal and concentration gradients.
This sulfation leads to expansion of the concrete, allowing further
ingress of materials to the reinforcing steel components. If water
condenses at the steel surface, FeS, forms causing rapid corrosion of
the steel and loss of mechanical strength of that particular compo-
nent. This could happen in the pit at temperatures .100
C (as the
water can adsorb and liquefy in the microstructures of the concrete)
or in locations where the steel will not be .100
C. Oxidation of the
FeS can further degrade the steel to iron oxides
Fe þ 1=8 S8 ƒƒƒƒƒƒƒƒƒ ƒ! FeS
condensed H2 O
To prevent metals corrosion in sulfur pits, water condensation and
concomitant acid production must be prevented. Claus process heating
system inside the pit shall also be effective to prevent condensation of
sulfur and water and hence mitigate the possibility of acid formation
(Fig. 4). The system must be inspected during regular testing and
inspections to assess the level of corrosion or repair any leaking
portions in the system. The porosity of concrete plays a major role in
controlling the ingress of the gas species and liquid inside the concrete
structure. A civil engineer or inspector should be employed in the plant
or consulted during repairs. Construction contractors in general are not
familiar with sulfur pit operation environment and the best repair
practices.
Acidic Attack
Two factors affect the consequences of acidic attack:
1. Spreading of acidic media in contact with concrete; and
2. Lowering alkalinity of cement-based materials.
To know how to protect the concrete and minimize damages, it is
valuable to know the mechanism and rate of acidic attack. When it
comes to acids, the actual concentration is more significant than the
pH value. The signs of acidic attack are loss of alkalinity, loss of
mass, loss of strength and rigidity. This is accompanied by a change
in compressive strength under formation of voluminous reaction
products.
The reactions include
1. Combination of sulfate with calcium ions during the hydration
of the cement to form gypsum
04014005-2 Pract. Period. Struct. Des. Constr.
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.

Fig. 3. Deterioration detailed chemistry

Fig. 4. Heating coils inside the pit

H2 SO4 þ CaðOHÞ2 → CaSO4 •2H2 OðgypsumÞ
2. Combination of the sulfate ion and the hydrated calcium
aluminate to form calcium sulfoaluminate (ettringite)
3CaSO4 þ 3CaO•Al2 O3 •6H2 O
þ 25H2 O → 3CaO•Al2 O3 •CaSO4 •31H2 OðettringiteÞ
These two reactions result in an increase of solid volume. Ettringite
formation is the cause of most expansion occurs to concrete caused
by sulfate solutions.
Thermal Expansion
The high temperature in the sulfur compartment causes the RC
structure to expand. This thermodynamic movement results in
structure deformation both horizontally and vertically. The com-
partment slab base arches upward and the side walls arch outward.
At the same time the concrete holding structure is restrained by the
surrounding backfill and this situation results in cracks formation.
On the other hand, high-temperature exposure desiccates the con-
crete and removes any free moisture within pores and capillaries.
This reduces ununiformly the volume of the exposed structural el-
ement and results in cracking.
Polymerization
In regions below the vapor zone, concrete changes into a harder and
denser material. When viewed under magnification, the altered
concrete is dark in color and its voids are filled with sulfur crystalline
structures. Compressive strength can double and in some cases

© ASCE 04014005-3 Pract. Period. Struct. Des. Constr.

Pract. Period. Struct. Des. Constr. 2014.19.

 triple. The polymerization of cemetitious products in contact with plasticizer [1:00 l ð100 kg21 Þ]. Cement=Silica fume=sand=water
molten sulfur is not well understood. 5 0:92:0:08:2:0:35.

Materials Selection Fiber Mesh Added to PC45

Cement
Concrete deteriorates in sulfur pits as its cement paste matrix is
chemically modified. A standard concrete mortar fraction can alter
and expand to .200% of its original volume under exposure to
sulfurous compounds. This is fatal to long-term concrete durability.
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.
This treatment is the same as PC45 except that polypropylene fiber
mesh (0:9 kgm23 ) was added to the mix.
PC45 Coated with Linseed Oil
PC45 specimens were given an external coating of linseed oil diluted
with diesel fuel (50% 3 volume). This method of protection has
been used for many years to protect concrete in bridges and other

According to the Portland Cement Association (PCA), two of the
five major types of portland cement can be used in sulfurous service:
• Type II (C3 A , 8%), moderate sulfate resisting; and
• Type V (C3 A , 5%), for severe sulfate-resisting service.
It is common practice to lower the W=CM ratio to increase du-
rability. However, lowering the W=CM ratio increases the cement
content of the mix, thereby increasing the tricalcium aluminate
(3CaO•Al2 O3 or C3 A). Supplementary cementing materials
(SCMs), such as slag, fly ash and silica fume, can be used to reduce
the portland cement content. SCMs reduce the concrete perme-
ability, decrease the cement content in the mix and decrease the
W=CM ratio.
Corrosion of Steel in Mortar Specimens Exposed to H2S
An experiment was carried out by researchers (Idriss et al. 2001)
after exposing mortar specimens to 2,000 ppm H2 S for 1 year. The
high concentration of 2,000 ppm was chosen to accelerate the test.
Six treatments were tested.
Portland Cement Type 10
Portland cement Type 10 (PC45) [Canadian Standards Association
(CSA 1994)] with 11% tricalcium aluminate (C3 A), W=C ratio is
0.45, Super plasticizer [0:125 l ð100 kgÞ21 cement], the weight ratio
of cement, sand, and water used in the mix design of specimens was
1:2:0.45.
Sulfate-Resisting Cement Type 50
C3 A content is 3.5%. All other factors were the same as PC45.
Silica Fume Cement
Eight percent of cement was replaced by silica fume W=C 5 0:35
(part of the cement is replaced by silica fume, which does not need
hydration water because it has no cementious properties), and super
road structures from corrosion. (This is not effective in sulfur pits
application and only mentioned because it was included in the
study.)
Portland Cement Type 10
Portland cement Type 10 with a W=C ratio of 0.55—it is only used to
demonstrate the inferior durability of concrete with this W=C ratio—
and no super plasticizer was used for this treatment.
The electrochemical potential test results revealed that silica
fume cement (SFC) exhibited the best corrosion resistance, followed
by sulfate-resisting cement Type 50 and fiber mesh added to PC4,
which were equally efficient in resisting H2 S.
Deterioration of Concrete Exposed to Sulfate
and Sulphide
An experiment was carried out by V. Assaad Abdelmseeh (Abdelmseeh
et al. 2008) to test the effect of sodium sulfate and sulfide on concrete.
One-half of 48 concrete specimens were partially immersed in
sodium sulfate (20,000 ppm SO22 4 ) and subjected to H2 S gas
(1,000 ppm H2 S). The second set was subjected to H2 S gas only.
The set consisted of eight different treatments including portland
cement (PC) concrete with 0.4 and 0:5 W=C ratios, PC concrete
with 8% silica fume replacement, 25% fly ash and 35% slag of the
total amount of cementing material and specimens made of PC
concrete with combinations of silica fume and fly ash (6 and 25%),
and silica fume and slag (6 and 25%). Finally one treatment was
carried out with sulfate-resistant cement. In all mixes a super-
plasticiser was used (625 mL per 100 kg of cementitious material).
Also an air-entraining admixture was used in all the treatments (50 mL
per 100 kg of cementitious material). The mix properties for all eight
treatments are shown in Table 1.
This experiment also revealed that the highest strength is
obtained with SFC (49.1 MPa), followed by PC 40 (48.6 MPa), and
SR (47.4 MPa).

Table 1. Concrete Mix Proportions and 28-Day Compressive Cylinder Strength (Reprinted from Biosystems Engineering, Vol. 99, No. 3, V. Assaad
Abdelmseeh, J. Jofriet, and G. Hayward, “Sulphate and sulphide corrosion in livestock buildings, Part I: Concrete deterioration,” pp. 372–382, 2008, with
permission from Elsevier)
PC50 PC40 SR SC SFC FAS SSFC FASF
PC with W=CM PC with W=CM Sulfate-resisting Slag Silica fume Fly ash Silica fume and Silica fume and
Concrete mix ratio 0.5 ratio 0.5 cement cement cement cement slag cement fly ash cement
Cement type 10 10 50 10 10 10 10 10
Cement (kg=m3 of concrete) 340 425 425 276 391 319 293 293
Water (kg=m3 of concrete) 170 170 170 170 170 170 170 170
W=CM ratio 0.5 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Additive (percentage of cementitious — — — 35% 8% Silica 25% Fly 25% Slag, 25% Fly ash,
material content) Slag fume ash 6% silica fume 6% silica fume

© ASCE 04014005-4 Pract. Period. Struct. Des. Constr.

Pract. Period. Struct. Des. Constr. 2014.19.

 These two experiments show that concrete with silica fume ce-
ment would have better performance under exposure to H2 S in sulfur
pits. Silica does not catalyze conversion of H2 S and SO2 to sulfur.
Hence, there is no formation of stable sulfates and acidic intermediates.
Lessons Learned in Design and Construction
Sulfur pits normally operate at temperature of ∼150
C. This is an
extremely severe environment for concrete structures (Fig. 5). De-
signers should understand and envision the conditions under which
sulfur pits operate. Provided specifications should be adequate to
ensure service durability of the structure. Decisions that might affect
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.
performance include, for example, specification of the cement type,
the selection of waterstop, detailing around sulfur pit concrete pen-
etrations, W=C ratio, concrete cover, and compartment thermal
growth, and the design for reinforcing to prevent corner cracking.
Most contractors are not familiar with the operating environment
of sulfur pits. Performance of the structure should not be left to the
contractor. The typical construction defects, such as incorrect
placement or absence of steel bars or waterstops, use of substandard
or inappropriate substitution of construction materials, can signifi-
cantly shorten the life of the structure. Stainless steel waterstop for
example, might get substituted with PVC, and Type-V cement
substituted with Type-I cement. Employment of wrong materials
and construction practices shortens the expected service life of sulfur
pits significantly.
The use of doweling adhesives in reinforcement repairs is not
recommended as the service temperatures exceed manufacturer
recommendations and doweling bars can be pulled out of drill hole
locations. Rebar coupling should be employed instead. Steel paint
products are also not recommended as service temperatures exceed
paint manufacturer recommendations. In this case the paint func-
tions as a bond-breaker between the steel and concrete. Though
stainless steel can be utilized as a liner, it is very expensive.
Use of epoxy-coated rebars in sulfur pits has been an issue in the
oil and gas industry because coating may melt because of the high
process temperature. However, some companies continue to use
epoxy coatings because of experience and results from reliability
studies.
On survey in the industry and review of the literature, there is no
industry-wide standard for sulfur pit design and construction. Some
hydrocarbon companies address sulfur pits construction in their
engineering standards; their knowledge and design criteria should be
Fig. 5. Sample of deterioration in pit opening
© ASCE 04014005-5
Pract. Period. Struct. Des. Constr. 2014.19.
captured and consolidated across the industry into a uniform design
guide.
Repair Strategies and Scenarios
Standard repair techniques are not sufficient in the repair of sulfur
pits. With a thermal shock of ∼90
C rise, even typical well-planned
repairs can fail immediately upon filling the sulfur pit with molten
sulfur products.
A proper repair strategy should consist of the following steps:
• Failure investigation and documentation (problem extent, loca-
tion, etc.);
• Root cause identification;
• Establishment of proper materials and repair procedure;
• Repair implementation by qualified and experienced personnel;
• Documentation for future reference (as-built drawings, mix
designs, material type, etc.); and
• Quality control and assurance.
The design/repair approach should address thermodynamic,
chemical, and material properties of the structure.
Based on the deterioration condition of the structure the required
repair can take many forms. This includes, but is not limited to, the
following (Kline 2006):
• Crack repair;
• Structural members repair;
• Construction of new protective lining; and
• Construction of a new structural liner.
Crack Repair
It is important to understand the mechanisms that result in structure
cracking. This ensures effective performance of the structure after
repair implementation. Chemically resistant and high temperature
tolerant materials should be specified for repairs. For the repair, typ-
ically cracks are grooved and the groove is impacted mechanically
with lead-wool. This is considered a reliable and durable repair. Lead
is a malleable metal with a melting point of 327
C, which is higher
than the normal sulfur pits’ operating temperature (∼150
C). The
typical approach to crack repair, that of simply gluing the concrete
members, is not effective. This is because concrete substrates and
crack interfaces are extensively contaminated with sulfurous pro-
ducts, making the repair procedure ineffective. Additionally, the high
temperature of sulfur typically volatizes resinous materials that are
generally employed in such repairs.
Structural Members Repair
In the repair of structural members it is important to select materials
that give composite behavior between the existing concrete and the
new repair materials. The application technique should ensure also
achieving adequate bond between the old concrete and the repair and
result in low shrinkage cracking. If evidence indicates significant
embedded steel corrosion, corrosion control measures need to be
applied.
Durability Liner
Liners applied in sulfur pits could be concrete, masonry, or metal
plating. Masonry and metallic liners do not allow visual examination
of the structural RC components. The existing condition of the
structure in this case is hidden from view, and assumptions must be
made to assess the structure condition. The deterioration can also
exacerbate behind these protective liners by trapping and concen-
trating sulfurous by-products.
Pract. Period. Struct. Des. Constr.
 Durability liners need to be engineered to provide significant
additional service-life to the concrete structure. To bond the repair
materials to the contaminated contact surface, mechanical anchor-
age needs to be used.
Structural Liner
A structural liner is used when the structure gets deteriorated to
a high risk of collapse. Different options are explored in this case.
These include process bypass (redirect the production to another
holding structure), new compartment construction or the construc-
tion of a new structural liner. Process bypasses are effective when
Downloaded from ascelibrary.org by University Of Wisconsin-Milwaukee on 01/30/15. Copyright ASCE. For personal use only; all rights reserved.
process piping can be assembled and molten sulfur storage is con-
tained using adjacent pits, tanks, etc. This is often a temporary so-
lution. Because of their congested areas, sulfur recovery plants do
not have enough space to construct new pits in the area. A liner is
considered a more practical long-term solution than repair (or re-
placement) of severely deteriorated pits. A structural liner some-
times referred to as a box-within-a-box or pit-within-a-pit, where
a new structure is designed and built within the old structure.
Conclusion
Concrete pits deteriorate based on chemical and environmental
factors. This deterioration may take the form of corrosion, sulfation,
acidic attack, thermal expansion, or polymerization. It is important
© ASCE 04014005-6
Pract. Period. Struct. Des. Constr. 2014.19.
to prevent water ingress inside the pit and prevent steam coils from
leaking to avoid sulfuric acid reactions. Previous experiments show
that lowering water/cement ratio concrete with silica fume additive
produces a durable concrete with higher corrosion resistance.
Designers must understand and envision the operation conditions
that affect pit durability. Contractors’ experience and materials se-
lection affect the structures’ performance significantly. All repairs
should be evaluated and conducted by specialized personnel with
a properly strategized and engineered procedure to implement an
effective and durable repair.
References
Abdelmseeh, V., Jofriet, J., and Hayward, G. (2008). “Sulphate and sulphide
corrosion in livestock buildings, Part I: Concrete deterioration.” Biosys.
Eng., 99(3), 372–381.
Clark, P., Dowling, N., and Bernard, F. (2009). “Corrosion pathways in
liquid sulfur run-down pits and other liquid sulfur handling facilities.”
ASRAL Quar. Bull. No. 150, 46(2), 16–37.
Idriss, A. F., et al. (2001). “Corrosion of steel reinforcement in mortar
specimens exposed to hydrogen sulphide, part 1: Impressed voltage
and electrochemical potential tests.” J. Agric. Eng. Res. 79(2), 223–
230.
Kline, T. R. (2006). Repair of subsurface molten sulfur containment
structures, Structural Preservation Systems, Hanover, MD.
Pract. Period. Struct. Des. Constr.