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    Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries
    Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries
    Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries
    Ebook331 pages4 hours

    Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries

    By James G. Speight

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    About this ebook

    According to NACE (National Association of Corrosion Engineers), the total annual cost of corrosion in petroleum refining takes up $3.7 billion in the US alone. Corrosion control is always a challenge for the downstream industry, but as the quality of feedstock is declining due to refineries accepting more of the heavy and shale gas and oil resources that are more readily available today, refinery managers, petroleum and natural gas engineers are unprepared for the new set of corrosion problems that are showing up in their equipment and processing units. Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries quickly gets the engineer and manager up to speed on the latest types of corrosion common for these lower grade crude oils and gases as well as the best prevention methods for all of the major sections of the refinery, especially desalting and sulfur recovery units, which are the most common problem areas for unconventional feedstocks. Also covering the unique midstream sections, or point of entry to the refinery, as well as the major critical refinery equipment, Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries offers the perfect quick cross-reference for the oil and gas community.
    • Gets engineers and managers up to speed on the latest types of corrosion common for lower grade crude oils and gases
    • Provides the best prevention methods for all of the major sections of the refinery, especially desalting and sulfur recovery units
    • Covers additional topics such as unique midstream sections, or point of entry to the refinery, as well as major critical refinery equipment
    LanguageEnglish
    PublisherElsevier Science
    Release dateMar 13, 2014
    ISBN9780128004159
    Oil and Gas Corrosion Prevention: From Surface Facilities to Refineries
    Author

    James G. Speight

    Dr. Speight is currently editor of the journal Petroleum Science and Technology (formerly Fuel Science and Technology International) and editor of the journal Energy Sources. He is recognized as a world leader in the areas of fuels characterization and development. Dr. Speight is also Adjunct Professor of Chemical and Fuels Engineering at the University of Utah. James Speight is also a Consultant, Author and Lecturer on energy and environmental issues. He has a B.Sc. degree in Chemistry and a Ph.D. in Organic Chemistry, both from University of Manchester. James has worked for various corporations and research facilities including Exxon, Alberta Research Council and the University of Manchester. With more than 45 years of experience, he has authored more than 400 publications--including over 50 books--reports and presentations, taught more than 70 courses, and is the Editor on many journals including the Founding Editor of Petroleum Science and Technology.

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    • 5/5
      Este libro trata de la Corrosion en las Refinerias y Planta de Gas. Moderno y de gran ayuda.
    • 5/5
      Good book.
      But it's too expensive to buy
      Thank you

    Book preview

    Oil and Gas Corrosion Prevention - James G. Speight

    Preface

    Dr. James G. Speight

    Laramie, Wyoming

    Corrosion can occur at any point or at any time during petroleum and natural gas recovery and processing. Thus is particularly true in ageing refineries and gas processing plants which can present a serious safety hazard.

    Key findings into corrosion processes in refinery equipment and gas processing plants as well as corrosion in offshore structures are presented.

    This book summarizes the key corrosion processes in refinery and gas processing equipment – such as storage tanks, reactors, and sour water strippers – and how it can be measured and controlled. Methods of testing for corrosion are presented as well as preventative measures. The book also contains a helpful glossary that will assist the reader in understanding the terminology of corrosion.

    December 2013

    Chapter 1

    Corrosion

    Corrosion is the deterioration of a material as a result of its interaction with its surroundings and can occur at any point or at any time during petroleum and natural gas processing. Although this definition is applicable to any type of material, it is typically reserved for metallic alloys. Furthermore, corrosion processes not only influence the chemical properties of a metal or metal alloys, but they also generate changes in their physical properties and mechanical behaviors.

    It is the purpose of this chapter to present the terminology of the different types of corrosion, as well as the key chemical aspects of corrosion processes and the types of corrosion that can occur in a refinery or gas processing plant.

    Keywords

    Chemistry; anodic reactions; cathodic reactions; acidic corrosion; sulfidic corrosion; oxidative corrosion; carburization; sour water corrosion; erosion–corrosion; crevice corrosion; crevice-galvanic corrosion; dealloying; biocorrosion; effect of temperature

    Note: This chapter is available on the companion website: http://store.elsevier.com/product.jsp?isbn=9780128003466&_requestid=1050998.

    1.1 Abstract

    Corrosion is the deterioration of a material as a result of its interaction with its surroundings and can occur at any point or at any time during petroleum and natural gas processing. Although this definition is applicable to any type of material, it is typically reserved for metallic alloys. Furthermore, corrosion processes not only influence the chemical properties of a metal or metal alloys, but they also generate changes in their physical properties and mechanical behaviors.

    It is the purpose of this chapter to present the terminology of the different types of corrosion, as well as the key chemical aspects of corrosion processes and the types of corrosion that can occur in a refinery or gas processing plant.

    1.2 Content

    1.1 Introduction

    1.2 Corrosion Chemistry

    1.3 Types of Corrosion

    1.4 Effect of Temperature

    Chapter e1

    Corrosion

    Corrosion is the deterioration of a material as a result of its interaction with its surroundings and can occur at any point or at any time during petroleum and natural gas processing. Although this definition is applicable to any type of material, it is typically reserved for metallic alloys. Furthermore, corrosion processes not only influence the chemical properties of a metal or metal alloys, but also generate changes in their physical properties and mechanical behaviors.

    It is the purpose of this chapter to present the terminology of the different types of corrosion, as well as the key chemical aspects of corrosion processes and the types of corrosion that can occur in a refinery or gas processing plant.

    Keywords

    Chemistry; anodic reactions; cathodic reactions; acidic corrosion; sulfidic corrosion; oxidative corrosion; carburization; sour water corrosion; erosion–corrosion; crevice corrosion; crevice-galvanic corrosion; dealloying; biocorrosion; effect of temperature

    1.1 Introduction

    Corrosion is a natural phenomenon and is the deterioration of a material as a result of its interaction with its surroundings (Fontana, 1986; Garverick, 1994; Shreir et al., 1994; Jones, 1996; Shalaby et al., 1996; Peabody, 2001; Bushman, 2002; Landolt, 2007). Although this definition is applicable to any type of material, it is typically reserved for metallic alloys. Of the known chemical elements, approximately 80 are metals (Figure e1.1) and approximately 50% of these metals can be alloyed with other metals, although the physical, chemical, and mechanical properties, and propensity for corrosion are all dependent upon the composition of the alloys. Furthermore, corrosion processes not only influence the chemical properties of a metal or metal alloys, but they also generate changes in physical properties and mechanical behavior.

    Figure e1.1 Periodic table of the elements.

    Furthermore, identification and understanding of the chemistry of corrosion can lead to the prevention of corrosion by preventing the predominant chemical reactions (Wranglen, 1985; Uhlig and Revie, 1985).

    It is the purpose of this chapter to present the chemistry, terminology, and key chemical aspects of corrosion processes, along with the types of corrosion that can occur in a refinery or gas processing plant.

    1.2 Corrosion Chemistry

    Metals occur either in the pure metallic state (the zero oxidation state: for example, iron would be represented as Fe⁰ in this state) or in the form of compounds with other elements (they acquire positive states of oxidation). The tendency of metals to corrode is related to the stability of the metallic state. Chemically, corrosion is an electrochemical reaction involving the movement of electrons: when steel is first exposed to the air, the original smooth surface of the zero oxidation state will be covered with rust in a relatively short time—perhaps even within a matter of hours (Figure e1.2). In actual fact, rust is not always composed of a single iron oxide, but is generally a mixture of ferrous oxide (FeO) and ferric oxide (Fe2O3), as well as complex oxides such as magnetite (Fe3O4).

    Figure e1.2 Representation of the chemistry of rust formation.

    1.2.1 General Chemistry

    Generally, when iron is used in an oxidizing atmosphere, corrosion is represented as the formation of rust (iron oxide), like what might occur in a pipeline (Beavers and Thompson, 2006) and which is often represented by the formation of iron oxide and then hydration in humid environments:

    In reality, rust formation is a much more complex process and occurs at the point of, or at some distance away from, the actual pitting or erosion of iron (Figure e1.2). The involvement of water accounts for the fact that rust formation occurs much more rapidly in moist conditions than in a dry environment (such as a desert), where water in the atmosphere or water in the ground is limited.

    Similarly, corrosion in a pipe (a pipeline or an intrarefinery transfer pipe) occurs when a negative area of metal (the anode) is connected to a positive area (the cathode) by the pipe wall itself. As a result, electrons can flow from the anode to the cathode (Chapter 3). In addition to the anode, the cathode, and the connecting conductive material, the electrochemical reaction requires one more element: the electrolyte. The electrolyte is a conducting solution and—in the case of a pipe—is the water within the pipe with its dissolved salts.

    Many other factors affect the chemistry and the rate of corrosion. For example, the presence of salt (sodium chloride, NaCl), like that which occurs in marine environments (Chapter 5), greatly enhances the rusting of metals because the dissolved salt increases the conductivity of the aqueous solution formed at the surface of the metal and enhances the rate of electrochemical corrosion. The sea and the salty atmosphere are saline media that are highly aggressive to metals: marine structures, such as drilling rigs, platforms, and marine pipelines, usually show signs of severe corrosion unless they have been properly protected (Chapter 5) (Dugstad et al., 1994).

    Another way of explaining corrosion—using the same chemical equations and resulting in the same effect—is through the agency of anodic and cathodic reactions. Any electrochemical reaction requires four elements, all of which must be in contact: (1) the anode, (2) the cathode, (3) the conductive material, and (4) the electrolyte. In the case of the corrosion of a pipe (Chapter 3), the anode, cathode, and conductive material are all found in the pipe wall, while the electrolyte is the water within the pipe. If any of these four elements, which make up the corrosion cell, are absent or are not touching each other, then corrosion cannot occur.

    1.2.2 Anodic Reactions

    The chemical reactions that take place in corrosion processes are redox reactions (reduction–oxidation reactions), which include all chemical reactions in which atoms have the oxidation state changed and generally involve the transfer of electrons between species. Such reactions require a material that is oxidized (the metal) and another that is reduced (the oxidizing agent). In the oxidation sequence (at the anode), the metal loses electrons. In the reduction reaction (at the cathode), the oxidizing agent gains the electrons that have been released from the metal.

    Oxidation of elemental iron occurs at the anode. First, the elemental iron breaks down, reacts, and then leaves the pipe, so pits form in the pipe’s surface at the anode:

    The following redox reaction is dictated by the availability of water and oxygen which are crucial to the formation of rust:

    In addition, the following multistep acid–base reactions and dehydration equilibria affect the course of rust formation:

    With limited dissolved oxygen, iron (Fe²+)-containing materials are favored, including ferrous oxide (FeO) and magnetite (Fe3O4). High-oxygen concentrations favor the formation of ferric (Fe³+) materials. The nature of rust changes with time, reflecting the slow rates of the reactions of solids.

    On an electrochemical basis, the rust builds up a coating over the anode’s surface. Ferrous hydroxide may then react with more water to produce another form of rust: ferric hydroxide [Fe(OH)3]. These layers of rust create tubercles (mounds on a metal surface that form a microenvironment), which can become problematic because they decrease the carrying capacity of the pipe and can be dislodged during high water flows, resulting in red water (water containing rust as a suspension). It should be noted that this is not the same reaction that turned the Nile red in Biblical times, which was due to an algal infestation of the river. The tubercles actually slow the rate of corrosion by preventing the electrolyte from interacting with the anode. If the tubercles are dislodged, the anode again comes in contact with water and the corrosion rate increases.

    1.2.3 Cathodic Reactions

    In cathodic reactions, the electrons from the breakdown of elemental iron flow through the pipe wall to the cathode. There, they leave the metal and enter the water by reacting with hydrogen ions and forming hydrogen gas:

    The hydrogen gas remains on the cathode and thereby isolates the cathode from the water by polarization. Just as the buildup of a tubercle breaks the connection between the anode and the electrolyte and slows the corrosion process, polarization breaks the connection between the cathode and the electrolyte and slows corrosion.

    Dissolved oxygen in the water is able to react with the hydrogen gas surrounding the cathode:

    This reaction (depolarization) removes the hydrogen gas surrounding the cathode and speeds up the corrosion process and, as a result, water that has a high content of dissolved oxygen is more corrosive than water with a low content of dissolved oxygen. By combining the electrical and chemical reactions, pipeline corrosion, in particular, involves a series of electrochemical events. Hydrogen gas will coat the cathode and separate it from the water by polarization.

    1.3 Types of Corrosion

    While corrosion (specifically rust formation) can be represented by relatively simple chemical reactions (shown above), that is not the complete story. There are various forms of corrosion, some of which involve redox reactions and many of which do not involve redox reactions (Garverick, 1994). These types of corrosion are presented (alphabetically) in the following sections.

    1.3.1 Acidic Corrosion

    Acid corrosion is typically (but not always) due to the presence of constituents in crude oil known as naphthenic acids, which is a generic name used for all of the organic acids present in crude oils and most of which arise as biochemical markers of crude oil origin and various maturation processes. Most of these acids are represented by simple chemical formulas, such as R(CH2)nCOOH, where R is a cyclopentane or cyclohexane ring and n is typically greater than 12. A multitude of other acidic organic constituents are also present in crude oil(s), but not all of the species have been fully analyzed and identified (Blanco and Hopkinson, 1983; Piehl, 1987, 1988; Fau, 1991; Babaian-Kibala and Nugent, 1999; Tebbal and Kane, 1996; Tebbal and Kane, 1998; Tebbal, 1999, 2000; Dettman et al., 2010; Speight, 2014).

    The acidic species in crude oil can be quantified by the total acid number (TAN) of the crude oil (Scattergood and Strong, 1987; Craig, 1995, 1996; Hau and Mirabal, 1996; Tebbal and Kane, 1996; Tebbal et al., 1996; Lewis et al., 1999; Kane and Cayard, 2002; Speight, 2014), which is expressed in terms of milligrams of potassium hydroxide per gram (mg KOH/g). The TAN is not specific to particular acid constituents, but refers to all possible acidic components of the oil and is the amount of potassium hydroxide required to neutralize the acids in one gram of oil. Alternatively, the base number can also be used (ASTM D974, ASTM D1386, ASTM D2896, ASTM D3242, ASTM D3339, ASTM D4739, ASTM D5770, ASTM D7253, ASTM D7389). The TAN usually refers to (organic) naphthenic acids, but mineral acids—such as hydrogen sulfide (H2S), hydrogen cyanide (HCN), and carbon dioxide (CO2)—also contribute significantly to corrosion of equipment. High-acid crude oils (HACs), also called high-total acid number (high-TAN) crude oils, are oils that typically have a TAN number in excess of 0.5. Processing HAC is also challenging for refineries, especially those not designed to handle crude oil containing naphthenic acids (Heller et al., 1963; Speight, 2014).

    Naphthenic acid corrosion is one of the serious, long-known problems in the petroleum refining industry (Derungs, 1956; Gutzeit, 1977; Slavcheva et al., 1998, 1999; Qu et al., 2005, 2006). The rates of naphthenic acid corrosion typically increase with increasing TAN or with increasing temperature. In the petroleum refining and the gas processing industries, factors associated with the composition and behavior of the feedstocks (such as temperature, TAN, fluid velocity, gas velocity, and pipeline/reactor material) work simultaneously and cumulatively. In order to obtain the credible corrosion rate, comprehensive analysis and estimation should be performed on the feedstock considering not only the temperature, but also any other relevant factors (Dettman et al., 2010; Ayello et al., 2011; Wang et al., 2011).

    Thus, naphthenic acid corrosion in the presence of hydrogen sulfide can be represented as:

    The first reaction produces the oil-soluble iron (iron naphthenate), and the second reaction inhibits soluble iron production: each reaction is dependent upon the functionality of the sulfur compounds (Meriem-Benziane and Zahloul, 2013). In short, the amount of sulfur in a crude oil (determined as total sulfur, S% w/w) is not necessarily related to reactivity. For example, hydrogen sulfide is very reactive toward iron, producing a protective layer of iron sulfide (FeS) that can prevent further corrosion by acidic species.

    Naphthenic acid corrosion is differentiated from sulfidic corrosion by the nature of the corrosion (pitting and impingement) and by the severe (naphthenic acid) corrosion at high velocity in distillation units. Feedstock heaters, furnaces, transfer lines, feed and reflux sections of columns, atmospheric and vacuum columns, heat exchangers, and condensers are among the types of equipment subject to this type of corrosion. Furthermore, isolated deep pits in partially passivated areas and/or impingement attack in essentially passivation-free areas are typical of naphthenic acid corrosion. In many cases, even very highly stable alloys (i.e., 12Cr, AISI types 316 and 317) have been found to exhibit sensitivity to corrosion under these conditions.

    1.3.2 Atmospheric Corrosion

    Atmospheric corrosion is the corrosion or degradation of metals exposed to the air and its pollutants, rather than to a liquid (as when immersed). It is one of the oldest known forms of corrosion and has been reported to account for more failures in terms of cost than any other single environment. The major form of such corrosion occurs in (1) dry environments and (2) wet or moist environments and is subject to several atmospheric and climatic variables.

    Atmospheric variables such as temperature, climatic conditions, and relative humidity, as well as surface shape and surface conditions that affect the time of wetness, are important factors that influence the rate of corrosive attack. Also, surface temperature is a critical variable: the corrosion rate increases sharply with an increase in the surface temperature of the metal, causing evaporation of the electrolyte, after which the corrosion rate increases even further. Metal surfaces located in areas where they become wet and retain moisture generally corrode more rapidly than surfaces exposed to rain. Rainfall has a tendency to wash the surface and remove particles of dust that can lead to differential aeration corrosion, with exceptions when metals are in areas that are subject to acid rain.

    The presence of sulfur dioxide and other sulfur-containing pollutants, which may be subject to seasonal or monthly variations, leads to a hostile (corrosive) environment and the formation of a less protective corrosion product film on normally passive metals. In locations in which sulfur-containing fuel is not burned during specific months of the year (such as winter months), this can lead to confusion during assessment of data from test methods (Chapter 6) performed during months that are not the climatic norm. The data may still prove to be valuable, but conclusions drawn from the data should take into account climatic conditions and climatic changes.

    1.3.2.1 Dry Corrosion

    Dry corrosion occurs in the absence of moisture and increases with increasing temperature. At ambient temperature, this form of corrosion occurs on metals that form a rapid thermodynamically stable film in the presence of oxygen. These films are desirable because they are typically free of defects and act as a protective barrier to further corrosive attack of the base metal; stainless steel, titanium, and chromium develop this type of protective film. Porous and nonadherent films that form spontaneously on nonpassive metals as unalloyed steel are not

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