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Sulfur Storage Pits in Petrochemical Plants: Deterioration Mechanism, Materials Selection, and Repair

Zakaria S. Alhelal 1

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 lm 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 signicantly 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 sul de; 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- de 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 ow considerations. Sulfur pits require steam heaters to maintain sulfur in liquid phase. Pits can be classi ed as working pits, with uctuating 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 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, H 2 O, SO 2 , and O 2 (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 H 2 O, O 2 , SO 2 , and other components that are present in the process gas. H 2 S is also present both as dissolved species, in the liquid sulfur, and also in chemical combination with sulfur

H 2 S þ S 8 H 2 S x

The air exists in the process to lower H 2 S concentration to an ac- ceptable and safe level. This causes oxidation inside the pit as H 2 S and H 2 S x oxidize and form H 2 O (Fig. 2)

H 2 S þ 1= 2 O 2 1= 8 S 8 þ H 2 O

Formation of SO 2 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.

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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 identi ed easily during regular testing and inspections. A portion of the pit wall may be bricked in 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, H 2 S, SO 2 , and O 2 . O 2 could be involved in direct oxida- tion of H 2 S to sulfur, resulting in sulfur formation inside the structure. Also H 2 S and SO 2 can be catalyzed within the holding structure by CaO to form sulfur and water (Fig. 3 ). SO 2 and O 2 are adsorbed by CaO surfaces and react slowly to form calcium sulfate CaSO 4 . High silica concretes, the preferred materials for sulfur concrete pit construction, also contain trace amounts of CaO, Na 2 O, MgO, and many other materials that can catalyze sulfur formation within the holding structure

can catalyze sulfur formation within the holding structure Fig. 1. Interior of holding structure ( Clark,

Fig. 1. Interior of holding structure (Clark, Dowling and Bernard 2009, with permission from ASRL)

2 H 2 S þ SO 2 3= 8 S 8 þ 2 H 2 O

Sulfur formed within the structure could be in liquid or solid form depending on the depth of its penetration. Solidication 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

condensed H 2 O

Fe þ 1= 8 S 8 ! FeS

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 signicant 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

ions during the hydration of the cement to form gypsum Fig. 2. T.O. sucks and burns
ions during the hydration of the cement to form gypsum Fig. 2. T.O. sucks and burns
ions during the hydration of the cement to form gypsum Fig. 2. T.O. sucks and burns

Fig. 2. T.O. sucks and burns gases from the pit ( Clark, Dowling and Bernard 2009 , with permission from ASRL)

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Copyright ASCE. For personal use only; all rights reserved. Fig. 3. Deterioration detailed chemistry Fig. 4.

Fig. 3. Deterioration detailed chemistry

rights reserved. Fig. 3. Deterioration detailed chemistry Fig. 4. Heating coils inside the pit H 2

Fig. 4. Heating coils inside the pit

H 2 SO 4 þ CaðOH Þ 2 CaSO 4 2H 2 O ð gypsumÞ

2. Combination of the sulfate ion and the hydrated calcium aluminate to form calcium sulfoaluminate (ettringite)

3CaSO 4 þ 3CaOAl 2 O 3 6H 2 O

þ 25H 2 O 3CaO Al 2 O 3 CaSO 4 31H 2 O ðettringite Þ

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 ther modynamic 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 backll 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 magni cation, the altered concrete is dark in color and its voids are lled with sulfur crystalline structures. Compressive strength can double and in some cases

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triple. The polymerization of cemetitious products in contact with molten sulfur is not well understood.

Materials Selection

Cement

Concrete deteriorates in sulfur pits as its cement paste matrix is chemically modi ed. 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. According to the Portland Cement Association (PCA), two of the ve major types of portland cement can be used in sulfurous service:

Type II (C 3 A , 8%), moderate sulfate resisting; and

Type V (C 3 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 Al 2 O 3 or C 3 A). Supplementary cementing materials (SCMs), such as slag, y 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 H 2 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 (C 3 A), W =C ratio is 0.45, Super plasticizer [0:125 l ð100 kg Þ 2 1 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 C 3 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

plasticizer [1 :00 l ð 100 kg 2 1 Þ]. Cement =Silica fume=sand= water 5 0 :92:0:08:2:0 :35.

Fiber Mesh Added to PC45 This treatment is the same as PC45 except that polypropylene ber mesh (0: 9 kgm 2 3 ) 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 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 aW= C ratio of 0.55it 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 ber mesh added to PC4, which were equally ef cient in resisting H 2 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 sulde on concrete. One-half of 48 concrete specimens were partially immersed in

) and subjected to H 2 S gas

(1,000 ppm H 2 S). The second set was subjected to H 2 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% y ash and 35% slag of the total amount of cementing material and specimens made of PC concrete with combinations of silica fume and y 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

sodium sulfate (20,000 ppm SO

22

4

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. 372382, 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

y ash cement

Cement type Cement (kg= m 3 of concrete) Water (kg= m 3 of concrete) W = CM ratio Additive (percentage of cementitious material content)

10

10

50

10

10

10

10

10

340

425

425

276

391

319

293

293

170

170

170

170

170

170

170

170

0.5

0.4

0.4

0.4

0.4

0.4

0.4

0.4

———

35%

8% Silica 25% Fly

25% Slag,

25% Fly ash,

Slag

fume

ash

6% silica fume 6% silica fume

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These two experiments show that concrete with silica fume ce- ment would have better performance under exposure to H 2 S in sulfur pits. Silica does not catalyze conversion of H 2 S and SO 2 to sulfur. Hence, thereis 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 specications should be adequate to ensure service durability of the structure. Decisions that might affect performance include, for example, specication 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 signi - 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 signicantly. 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

standards; their knowledge and design criteria should be Fig. 5. Sample of deterioration in pit opening

Fig. 5. Sample of deterioration in pit opening

captured and consolidated across the industry into a uniform design guide.

Repair Strategies and Scenarios

Standard repair techniques are not suf cient in the repair of sulfur pits. With a thermal shock of 90 C rise, even typical well-planned repairs can fail immediately upon lling 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 identication;

Establishment of proper materials and repair procedure;

Repair implementation by qualied 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 specied 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 pitsoperating 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 signicant 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.

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Durability liners need to be engineered to provide signi cant 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 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

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 structuresperformance signi cantly. 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), 372381. 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), 1637. 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.

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