Sulfur Pit Assessment and Repair Strategies

By: Thomas R. Kline

Division Manager, Engineering Services
STRUCTURAL TECHNOLOGIES

INTRODUCTION
One aspect that is true of all crude oil types is that each has differing amounts of sulfur content.
However, the sulfur is not in the form of elemental sulfur a chemical all by itself but is usually in
the form of a sulfur compound. Due to its odiferous and environmentally objectionable nature, sulfur
removal from hydrocarbons before the product gets to the burner tip is the focus of a Refinerys Sulfur
Recovery Unit (SRU).

Typically, the industry references to crude oils of varying sulfur content is to categorize them into
sweet and sour crudes. It is interesting to note that in the early days of Pennsylvania crude
oil production, petroleum was primarily sought to make kerosene as a substitute for the whale oil
used as lamp oil for indoor lighting. If a kerosene fraction had too much sulfur, it would have an
unacceptable smell when burned. Somewhere along the line, someone discovered that kerosene,
with higher sulfur content, had more of a sour taste and kerosene with a low sulfur content had a
sweeter taste. Today, typically sweet crudes have 0.05% or less sulfur content while sour crudes have
1.5% or more sulfur by content. Generally, the area in-between is sometimes called intermediate
sweet or intermediate sour.1

Once extracted from the crude oil fraction in

refineries, the sulfur is conveyed in molten
form and stored in a variety of different type
of vessels. These vessels can be constructed
of carbon/stainless steel, aluminum-alloy
or reinforced concrete. The vessels can be
mobile, such as in marine barges, railroad train
cars and tanker trucks. However, stationary
vessels, such as above-grade insulated
storage tanks, can be constructed of carbon/
stainless steel and/or aluminum-alloy. Below-
Figure 1 - Below grade sulfur pit
grade storage vessels, usually required due to
gravity process flow considerations, are almost
always conventionally reinforced concrete
pits/tanks. There are typically two types of below-grade sulfur pits that include working pits (i.e. day
pits or sumps with daily fluctuations in molten sulfur levels) and storage pits that maintain relatively
consistent molten sulfur levels. The focus of this paper will be the condition assessment and repair of
below-grade conventionally reinforced concrete pits designed and constructed for the handling and
storage of molten sulfur (Figure 1).
BACKGROUND
To better understand the aggressive environment of an operating below-grade sulfur pit is to realize
that molten sulfur must be kept fluid, usually by submerged heating coils, at a temperature ranging
from 250oF (121oC) to 300 oF (149 oC) in essentially a dry environment. Impurities within the sulfurous
compounds, such as Carsul, are heavier than elemental sulfur and settle-out and deposit at the
base of these sulfur storage vessels and over time, hinder the effectiveness of the heating elements.
Inconsistent heating of molten sulfur creates significant heating gradients that form warm and cool
areas within the sulfur storage pit. It should be noted that areas within a sulfur pit primarily affected by
deterioration exist within a region known as the vapor zone. The vapor zone exists above the molten
sulfur level and can contain atmospheric gases including water vapor and oxygen.

STRUCTURAL CONSIDERATIONS
Structural considerations associated with below-grade sulfur storage vessels involve thermal growth
of the reinforced concrete sulfur pit reacting against densely compacted backfill materials. These
thermodynamic movements result in deformation of the structural section both laterally and vertically.
Essentially, the pits base slab arches upward and its sidewalls bulge outward to accommodate these
irresistible forces as shown in Figure 2. Unfortunately,
the immovable object, in the form of compacted backfill, 57o F
provides restraint against these forces and cracks
ultimately form within the reinforced concrete structural
section while in operation.

CONCRETE COMPOSITION AND QUALITIES 300o F

Concrete, as a construction material, is best thought
of as castable stone of many blended constituents
(i.e. heterogeneous) that forms the worlds most
versatile building product. This mixture combines
sand, cement, stone, water and admixtures forming a
hardened mass. Although very good in compression,
concrete as a material is weak in tension. Therefore, a Figure 2 - Thermodymanic movements
structural concrete member requires the integration of
reinforcement, usually in the form of deformed steel bars,
to create a composite structural section capable of carrying compressive and tensile loads. In an
aggressive sulfur pit environment, special protective properties are required of the concrete to resist
extreme swings in temperature, acidity and embedded metal corrosion.

Concrete provides protection within the aggressive sulfur pit environment through mixture density
and appropriate blending of specialty Portland Cements that are low in tricalcium aluminate (C3A).
According to the Portland Cement Association (PCA) two of the five major types of Portland Cement
can be used in sulfurous service which include Type II (C3A<8%) moderate sulfate resisting and Type
V (C3A<5%) for severe sulfate resisting service2. For sulfur pit service, designers typically specify
that Type V Portland Cement be incorporated into the concrete mixture as well as the addition of
one or more mineral admixtures such as Flyash, Microsilica, or other finely ground pozzolans (i.e.
non-reactive volcanic ash, etc.). Occasionally, Hydraulic Cement based products such as Calcium
Aluminate Cement or unconventional Portland Cements incorporating high fractions of blast-furnace
slag and/or pozzolans are also specified for concrete sulfur pit construction. Aggregate selection
must incorporate non-reactive and chemically resistant properties. Consistent ready-mix concrete

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properties of the various concrete types reveal a common thread that includes low water/cement
ratios, specified strengths above 4,000 PSI and extended curing that forms a more impermeable
finished product.

CONCRETE MATERIAL ALTERATION

Aggressive concrete service and subsequent deterioration can mean many different things. In a
sulfur pit environment, concrete deterioration is characterized by the concrete cement paste matrix
being chemically modified and no longer exhibiting properties consistent with structural support/
containment. Essentially, the concrete mass, altered by exposure to sulfurous products, undergoes
chemical reactions that expand the concrete mortar fraction. This resulting expansion always proves
fatal to long-term concrete durability. The reactions include:
Combination of sulfate with calcium ions liberated during the hydration of the cement to form
gypsum. (CaSO4 32 H2O)
Combination of the sulfate ion and the hydrated calcium aluminate to form calcium
sulfoaluminate (ettringite). (3CaO Al2O3 3CaSO4 3H2O)

Both of these reactions3 result in an increase in solid volume. The formation of ettringite is the cause
of most of the expansion and disruption of concrete caused by sulfate solutions. Although expanding
in volume during chemical attack and as a result of thermal growth due to elevated temperatures
associated with keeping elemental sulfur molten, reductions in volume also occur concurrently.
High temperature exposure desiccates the concrete removing any free moisture within pores and
capillaries within the concrete - ultimately reducing the volume of the exposed structural element.
Unfortunately, this reduction in size is not uniform and various areas experience restraint which then
stress-relieve themselves by cracking.

Another process that occurs but that is less well understood, is that of polymerization of cemetitious
products in contact with molten sulfur. In regions below the vapor zone, concrete construction
materials actually change into a harder, more dense product. When drilling or coring concrete in
these regions, diamond and tungsten tipped drill tools can dull and blue flames emerge from drill/core
locations. Compressive strength testing of collected core specimens has verified that the concrete
can double and in some cases triple in compressive strength. When viewed under magnification, the
altered concrete is dark in color and voids filled with sulfur crystalline structures. Although not truly a
Sulfur Concrete as described in the American Concrete Institute Committee 548 (Guide for Mixing
and Placing Sulfur Concrete in Construction), characteristics such as high compressive strengths are
shared by both types of concrete.

CONCRETE DETERIORATION MECHANISMS

In the concrete repair industry there is an adage There are three things you can count on with
concrete and they are: 1-Concrete holds up well in a fire; 2-No one will steal your concrete; and
3-Concrete cracks. Although somewhat humorous, the last part of the adage is true and we, as
concrete professionals, must do our best to minimize the amount and extent of cracking. Cracks can
form by various processes including:
Material Shrinkage
Structural Overload
Thermal Restraint
Chemical Reactions
Freezing and Thawing
Embedded Metal Corrosion
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Once cracks form, regardless of the mechanism, the relatively impervious protection afforded by
the concrete cover is compromised and secondary effects of concrete distress initiate as a result. In
subsurface sulfur pits, cracks in many cases, extend through the entire structural section allowing
groundwater ingress into the molten sulfur cavity. As the groundwater migrates through the wall, it
contacts embedded reinforcing steel setting up microcell & potentially macrocell corrosion activity.

During embedded steel corrosion activities, the steel metallurgy changes, with corrosion products
requiring and occupying more space than the parent material. As such, significant tensile stresses are
exerted on the concrete in the immediate proximity of the corroding steel. As stated earlier, although
inherently strong in compression , concrete is relatively weak in tension; therefore, unrestrained
portions of the concrete mass (i.e. protective cover overtop of embedded reinforcing steel) will crack
at the corroding rebar interface. Close examination of cracked concrete in the proximity of corroding
reinforcement reveals radial cracking with corrosion products occupying the annular space of the
crack fissure. The wedging effect of corrosion products along planes of reinforcement form internal
separations (i.e. delaminations) within the mass that eventually leads to cross-section detachment
of the concrete from the parent substrate (ie. spalling). Once this cover detaches, oxygen and
moisture become abundantly available to fuel the corrosion process. The progression from crack-to-
delamination-to-open spall accelerates the electrochemical processes of corrosion and can result in
cases of diminished durability and structural integrity.

We spoke earlier of concrete matrix alteration due to chemical processes, but the end result of this in
regions within the vapor zone is the formation of a semi-gelatinous mass incapable of transmitting or
supporting loads compressive or tensile. Although generally unaffected below the vapor zone of an
operating sulfur pit, reinforcing steel bars loose the critical bond required for composite action of the
structural cross-section. Also, daily vertical movement of molten sulfur levels provide a scouring effect
in working pits that essentially abrade the semi-gelatinous mass over time. After cleaning sulfur pits
for inspection purposes, it is not uncommon to find piles of fine and coarse aggregate along with relic
indicators of rebar within wall cavities where fully reinforced concrete wall sections once stood.

CONSTRUCTION/DESIGN DEFECTS
When we review structures experiencing distress, many times the distress is related to defects
associated with original construction. Defects can range from substandard or inappropriate
substitution of construction materials, incorrect placement or absence of embedded rebar or
waterstops, insufficient consolidation of freshly placed concrete, inadequate curing and lack of
detailing around sulfur pit penetrations.

Design defects generally relate to designers inability to envision the harsh operating environment of
a sulfur pit by providing poor or inadequate specifications with a lack of focus on service durability.
Frequently designers leave the sulfate resistance decisions to the contractor in the form of a
performance specification. Unfortunately, most new construction contractors have even less of a
clue as to the operating environment of a sulfur pit than the specifying engineer. Quality construction
materials (i.e. stainless steel, aluminium-alloys, etc.) are seen as an unneeded expense and
substitutions are frequently allowed at the time of construction. It is not unheard of, during the
construction of a new sulfur pit, to have PVC waterstops substituted for stainless steel and Type V
Portland Cement substituted by Type I/II Portland Cement in the concrete mix design with these
substitutions thought to be equivalent. Our experience has shown us that in as little as 6 years, if the
wrong materials and construction practices are employed, a sulfur pit will fail prematurely in service.
Conversely, sulfur pits over 40 years in age, when inspected, appear to be in excellent condition and
apparently ready to provide an additional 40 years of service.

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REPAIR FAILURES
Many times SRU Operators are faced with tough decisions during short duration outages as to
what to do during periodic sulfur pit inspections, when damage is detected in their sulfur pit. To
an untrained eye, using standard repair techniques in such instances would suffice until the next
outage, anywhere from 3 to 8 years away. Unfortunately, when approached in this manner, repairs
typically fail immediately upon filling the sulfur pit with molten sulfur products (Figure 3). Essentially,
assumptions are made by specifiers and product manufacturers that do not take into account
groundwater seepage, the depth of contamination/alteration that sulfurous products have upon
concrete and the behavior of relatively green repair materials trying to bond to a hardened substrate.
Ultimately, the repair system, in short order, is thermal shocked by an approximate 200oF temperature
rise; harsh for even well-planned repair programs.

Discussed earlier in this paper was the formation of cracks within the reinforced concrete section due
to the structural behavior of the sulfur pit in service. Should groundwater be present at significant
levels surrounding the sulfur pit, this water will find its way into the sulfur pit cavity via crack fissures.
These water sources are unwelcomed in repair
construction as they create water channels
extending through the entire structural section
during fresh concrete placement. Industry
standard waterproofing practices provide poor
functionality once the sulfur pit enters service
as the expansive polymer resin systems
installed are not recommended for service
conditions above 140oF.

Testing has shown that all concrete, to some

extent is altered by contact with molten sulfur. It
is probably best to think of concrete as a hard
sponge, that although it can maintain a high
compressive strength, concrete is really porous
allowing vapor to penetrate its capillaries and
voids. Therefore, for sulfur pits in service, Figure 3 - Failed sulfur pit repairs
there is no such thing as an uncontaminated
contact surface onto which you can chemically
bond a repair material without the addition of
mechanical anchorage. The term mechanical anchorage is important to note as the use of polymer
adhesive anchors are not recommended as they have glass transition points at or below operating
sulfur pit temperatures. Consequently, the adhesives will volatize in-service and/or creep under load.

During short duration outages, repair products need to be placed and consolidated quickly, integrate
with adjacent existing concrete substrate materials, cure and outgass rapidly (i.e. dissipation of
uncombined and free water), attain strength and durability characteristics quickly and have very low
material shrinkage characteristics. Generally, products that meet the aforementioned criteria are
prebagged proprietary blends of cementitious materials developed for extreme sulfate resistance
and are contractor placement friendly. Friendly repair materials are usually castable as the use
of pneumatically placed shotcrete in confined spaces generally provide too great of an opportunity

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to incorporate contaminants into the structural section. Contaminants such as rebound (ie. spent
unhydrated shotcrete materials) create voided conditions and consequently a porous and ineffective
structural section. The installation of sawcut repair edge treatments is always applicable to provide
containment due to initial thermal shock and a consistent repair cross-section (ie. no feather-
edging).

Reestablishment of reinforcing steel integrity does not always allow for lap splicing within sulfur pits
due to short exposed rebar lengths. The use of doweling adhesives are also not recommended as
the service temperatures exceed manufacturer recommendations. It is not uncommon to inspect
previously repaired sulfur pits and be able to pull doweling bars out of drill hole locations with only
relic indicators of what once was a resinous adhesive compound along the circumference of the
rebar. Consequently, coupling technology must be employed otherwise the reinforcement continuity
will be compromised. Also, the use of cathodic protection for embedded reinforcing systems, active
or passive, is strongly recommended for sulfur pit repair programs that address significant corrosion
processes. Corrosion inhibiting reinforcing steel paint products are not recommended as complete
coverage of embedded reinforcing steel bars is rarely possible. Additionally, the paint, when dripped
onto prepared concrete substrates, functions as a bond-breaker and sulfur pit service temperatures
exceed paint manufacturer recommendations.

CONCRETE REPAIR PROCESS

History and experience have shown that each sulfur pit can pose unique challenges to a repair
contractor. Regardless of whether it is full-depth, a partial liner, or stopping water ingress, it is
imperative to utilize an engineered solution. A proper repair strategy should consist of the following
elements:
Identifying and determining the root cause of the failed concrete;
Employing proper materials in construction and repair techniques; and
Using a qualified, experienced contractor who can provide a solution, as well as a well-planned
quality assurance and control program (QA/QC), for the repair.

These three steps will assure the SRU manager that the repair-failure-repair cycle can be eliminated
and a sound structure put back into operation4. A more comprehensive view of how these steps
translate into the repair process is shown in Figure 4.

CONDITION SURVEY/FORENSIC
INVESTIGATION
Condition Assessments have on occasion been
likened to being locked in a dark closet with an
animal you may hear it, smell it, grab portions
of it, but ultimately you do not know the full
picture of the animal until the light goes on and
all the pieces come together. Similarly, concrete
deterioration comprises both obvious and latent
characteristics that are not easily understood
without gathering further information through
investigation.
Figure 4 - Concrete Repair Process

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To detect the cause and the degree of concrete deterioration within a sulfur pit, a Condition Survey
and Evaluation are conducted on-site. This step requires a high degree of specialization and wide
ranging experience to correctly assess the complexity and severity of a problem. Use of cutting-edge
analytical and diagnostic tools the evaluator establishes these repair parameters:
An evaluation that investigates further, and qualifies causes and effects;
A quantification of the problem that expresses its extent in concrete terms (e.g. square feet,
cubic feet, linear feet, etc.); and
Documentation describing where the distressed conditions are located and what it will cost to
repair them arranged from highest to lowest priority.

Unlike forensic efforts in other process units, the molten sulfur environment is too hostile for an in-
process evaluation. However, techniques have been developed to assess quickly causes and effects
of concrete deterioration, once the sulfur pit has been cleaned and made available for inspection
during a short duration outage. Employing a combination of Non-Destructive Testing (NDT) and
Semi-Destructive Testing (SDT) techniques, characterizations as to the physical and chemical
characteristics can be determined quickly and the Owner debriefed as to the existing condition of the
sulfur pit. NDT methods include:
Visual Inspection (Noting areas of concrete cracking, delamination, spalling and other
significant features);
Acoustic Impact TestingASTM D 4580-(Mechanical Sounding of accessible surfaces in an
effort to detect subsurface voids and/or delaminations);
Pachometer Survey (Electromagnetic detection of embedded reinforcing steel bars within the
hardened concrete mass);
Rebound Hammer Testing-ASTM C 805-(Surface Hardness Testing of concrete for rapid
comparison of consistency and quality determinations);
Ultrasonic Pulse Velocity Testing-ASTM C 597-(Method employing low-frequency mechanical
energy based on physical laws of elastic stress wave propagation in solids to rapidly evaluate
relative quality and compressive strength of hardened concrete).

SDT methods include:

Concrete Core Sampling ASTM C 42-(Employing wet rotary diamond core drilling techniques,
remove representative concrete samples for further examination and testing);
Drill Probe (Rotary Hammer Drill Method used to qualitatively determine the extent of unsound
concrete and collect concrete powder samples).

Once samples are secured, cataloged and prepared, laboratory testing is performed on the
specimens which can include:
Depth of Carbonation (Method of testing that involves the use of phenolphthalein indicator
solution sprayed onto freshly fractured concrete that provides an indicator of the existing
concrete and current susceptibility to corrosion activity);
Chloride Ion Content of Hardened Concrete Test ASTM C 1218-(Test results determine the
chloride ion (Cl-) level within the concrete. The detected level is an indicator of the potential

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 electrochemical process of embedded metal corrosion within the concrete mass).
Compressive Strength Testing of Concrete Core Specimens ASTM C 42-(Test results provide
strength values and are indicators of the relative quality of the concrete).

SULFUR PIT REPAIR SCENARIOS

Below-grade sulfur pits come in various shapes and sizes and are installed in diverse geographical
regions and in varying terrain. These structures have unique pedigree based on design, who built
them, where they are located and how they are maintained. So it is not hard to envision that when
these structures experience distress, special opportunities exist for formulating strategic repair
approaches. A partial listing of difficult distress conditions and successful repair approaches include:
Leaking Cracks Chink leaking cracks with lead wool mechanically driven into sawcut crack
cavities. This process is a derivative of leaking crack repair techniques used successfully by
concrete tunneling contractors. Developed in the 1800s, chinking materials of construction
are resistant to high process temperatures associated with sulfur pit operation where
modern expansive polymers and cementitious water-stopping grouts volatize and dessicate,
respectively.
Waterstop/Joint Failure Using high temperature resistant sheet elastomers, mechanically
batten sealing strips or embed into concrete using cementitious anchorage materials, failed
waterstops and leaking joints can be addressed for positive side waterproofing.
Groundwater Ingress Reduction in groundwater levels below the sulfur pits base slab
elevation can address leaking water conditions with the use of Well Points. This option is rather
extreme as typically the collection water requires treatment and when the Well Point system
is shut down, the groundwater level rises to original levels. As such, the Well Point system will
require continuous operation and regular maintenance.
Corroded Reinforcement Reestablishing reinforcing steel bar integrity typically means the
lapping of new steel bars of appropriate lap length at each location when metal corrosion
losses exceed 20% or as determined by a Structural Engineer. However, due to short structural
member repair heights/lengths, lap length splicing is frequently limited. Fortunately, mechanical
coupling technology exists to splice onto sound existing rebar and maintain continuity
throughout the repair.5
Surface Erosion/Spalling Repair of concrete section losses requires adequate repair cavity
preparation. The process includes sawcut repair cavity perimeters, undercutting of exposed
reinforcing steel bars, abrasive grit/high pressure water blasting of resultant excavated
surfaces, installation of mechanical anchorage system, installation of a corrosion mitigation
system and reestablishment of the concrete cross-section. Specialized installation techniques
using Form and Pump or Form and Pour for castable sulfate resisting cementitious concrete
repairs provide a verifiable quality assurance/quality control (QA/QC) audit trail and assure
repair composite behavior. Guidelines established by the International Concrete Repair
Institute (ICRI) and the American Concrete Institute (ACI)6 provide various concrete repair
industry standards to assist Owners, Engineers and Contractors in providing a long-term,
durable repair solution.
Loss of Structural Integrity Occasionally, sulfur pits experience distress conditions so
advanced that conventional repair construction will not provide an adequate Return-On-
Investment (ROI) to bring the pit back to a serviceable condition. In cases such as these, a
new pit-within-a-pit scenario should be considered as an option. Essentially, the existing

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 concrete sulfur pit is considered rigid backfill and the new reinforced concrete sulfur pit is
modeled and structurally designed accordingly to address thermodynamic behavior with
surrounding geotechnical information obtained by test borings. Developing geotechnical
information is key as the reaction of the concrete sulfur pit against surrounding backfill
materials establishes structural design requirements for reinforcement and concrete cross-
section.

As can be seen above, sulfur pits provide especially difficult challenges for long-term repair programs.
Thermodynamic, chemical and construction material properties of the structure operating within the
aggressive molten sulfur service environment require a thoughtful and detailed repair approach.
Market surveys of the sulfur generation/storage/rehandling industry reveal literally hundreds of these
types of structures in North America alone and international experience has shown that concrete
sulfur pit deterioration has similar root cause mechanisms regardless of worldwide location.

REFERENCES
1. Leffler, William L., Petroleum Refining In Nontechnical Language, 3rd Edition, Penwell
Corporation, Tulsa, OK, 2000.
2. Kosmatka, Steven H., Panarese, William C., Design and Control of Concrete Mixtures,
Portland Cement Association, 13th Edition, Portland Cement Association, Skokie, IL, 1988, pgs.
15-17.
3. Guide to Durable Concrete, ACI Manual of Practice, Part 1, ACI 201.2R-92, American
Concrete Institute, Detroit, MI, 1998.
4. Schwabenlander, R., Kline, T., Sulfur-Recovery Operations Pose Formidable Challenge to
Concrete Infrastructure, World Refining, Vol.12/No. 4, May 2002, pgs. 30 & 31.
5. Manual of Standard Practice, 27th Edition (MSP-2-01), Concrete Reinforcing Steel Institute,
Schaumburg, IL, 2001, pgs. 4-4 & 4-5.
6. Concrete Repair Manual, 1999 Edition, Published jointly by the International Concrete Repair
Institute, Sterling , VA and the American Concrete Institute, Farmington Hills, MI, 1999, 861
pgs.

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