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Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Oil & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Over time, recommended best practices for crude unit materials selection have evolved to accommodate new operating requirements, feed qualities, and product qualities. The shift to heavier oil processing is one of the major changes in crude feed quality occurring over the last 20 years. The three major types of crude unit corrosion include sulfidation attack, naphthenic acid attack, and corrosion resulting from hydrolizable chlorides. Heavy oils processing makes all three areas worse. Heavy oils have higher sulfur content; higher naphthenic acid content; and are more difficult to desalt, leading to higher chloride corrosion rates. Materials selection involves two major criteria, meeting required safety standards, and optimizing economics of the overall plant. Proper materials selection is only one component of a plant integrity approach. Materials selection cannot eliminate all corrosion. Proper materials selection requires appropriate support from other elements of an integrity protection program. The elements of integrity preservation include: materials selection (type and corrosion allowance); management limits on operating conditions allowed; feed quality control; chemical additives for corrosion reduction; and preventive maintenance and inspection (PMI). The following discussion must be taken in the context of the application of required supporting work in all the other areas. Within that context, specific materials recommendations are made to minimize corrosion due to the most common causes in the crude unit.

1. Introduction
Materials selection for crude units must take into account three major corrosion mechanisms;  Sulfidation.  Naphthenic acids.  Hydrolizable chlorides. Other mechanisms can occur, but are much less common. The order presented follows along with the occurrence of the problem as crude oil progresses through the unit. It is also the order of complexity in the choices possible. Sulfidation issues are relatively straightforward. Chloride issues are much more complex. Historically, carbon steel has been the base metallurgy for crude unit equipment and piping. Even today, carbon steel is typically considered the base metallurgy choice because of its low cost. With a sufficient corrosion allowance and implementation of appropriate preventive maintenance and inspection (PMI), carbon steel remains an acceptable choice for much of the crude unit. Specific corrosion mechanisms will be considered as how they require a deviation from the standard carbon steel choices.

2. Sulfidation
Sulfidation is the simplest mechanism in crude corrosion. Corrosion rates are strongly related to operating temperature and sulfur content of the crude. The relationship is reliable in general trends. Solutions are also straightforward. Chrome alloys provide good to excellent resistance to sulfidation corrosion. Materials selection with appropriate PMI is nearly always used. Sulfidation attack occurs when the hydrogen sulfide reacts with iron in the steel. Sulfidation corrosion is typically a general corrosion. Metal loss occurs fairly evenly over the entire surface of the equipment. It is worse in

______________________________ 1 P.E., Principal Engineer – Process – CH2M HILL

Rio Oil & Gas Expo and Conference 2012 areas that have high velocity. What determines the attack rate is the metal temperature at the contact surface. Equipment that heats oil has higher metal surface temperatures than the bulk temperature. Equipment that cools oil has a lower metal surface temperature than the bulk temperature. For heating services, corrosion rates and materials selections should be conservative compared to reported data. Conversely, materials choices can be less rigorous in cooling services. Carbon steel adequately resists sulfidation attack below 0.2 weight percent sulfur in the oil and 232°C (450°F) bulk temperatures. Once above 0.2 weight percent sulfur and above 232°C (450°F), sulfidation corrosion must be considered. McConomy (1963) derived curves that plotted corrosion rate versus temperature at 0.6 weight percent sulfur. These curves were developed from 1960s industry data, mainly from heater tubes. The original curves should still be used for selection of heater tube material. Later work by Gutziet (1986) modified these curves to make them less conservative and applicable to regular piping and vessels. Both the original and the modified curves should be considered approximate. Based on actual oil composition and processing conditions, corrosion rates 10 times higher (or more) than the modified McConomy curves have been reported. 2.1 Materials Selection One legitimate choice with sulfidation corrosion is to increase corrosion allowances and put a PMI program in place to monitor corrosion rates. Carbon steel is generally considered an acceptable choice for crude unit equipment upstream of the desalter and even through most pre-flash columns or towers. This assumes a pre-flash operating temperature of 232°C (450°F) or less. Chromium adds the key element of corrosion resistance against sulfidation for ferrous metal components. As a practical matter, cost considerations tend to focus crude unit materials on four alloys; 5-Cr, 9-Cr, 410SS, and 304SS. While other materials are available, experience has shown the cost break points on these alloys as the most attractive. Table 1 shows relative corrosion rates to sulfidation attack at 315°C (600°F). Carbon steel is shown as a rate of one. Table 1 Relative Corrosion Rates – Sulfidation (Modified McConomy curves – 0.6 weight percent sulfur) Material Relative Corrosion Rate, at 315°C (600°F) Cost Carbon Steel 1.000 Increasing 5-Cr 0.22 9-Cr 0.12 410SS (12% Cr) 0.035 304SS (18% Cr) 0.008 Roughly, once 12% chromium is reached, sulfidation corrosion is rarely an issue even with a typical ~1.5 mm (0.0625”) corrosion allowance for alloy components. The exact break of where to switch from one alloy to another will depend upon peak versus average sulfur levels, sulfur species, expected operating conditions, and PMI programs in place. General recommendations are;  Carbon steel is acceptable to temperatures up to 230°C (450°F), above that chrome alloys are required.  5-Cr alloys are suitable for most operations up to 315°C (600°F) and two weight percent sulfur in the oil.  9-Cr alloys are suitable for most operations up to 400°C (750°F) and five weight percent sulfur in the oil. Higher sulfur contents can be tolerated with a sufficient corrosion allowance.  410SS and 304SS resist sulfidation corrosion across all ranges of operation found in typical crude units. Each of these alloys has other characteristics that can affect material selection. These recommendations are more conservative than those shown in API RP 939-C (section 7.2.2) for selection of materials for resistance to sulfidation (API 939C 2009). Heavy crudes have higher sulfur contents and should have more conservative materials selection. 5-Cr and 9-Cr alloys require post-weld heat treating. This makes fabrication more expensive. In small diameter systems (50 mm, 2-inch NPS and under), 304SS may be cheaper because it does not require post-weld heat treating. Piping and equipment with 5-Cr and 9-Cr must be properly identified and management controls in-place to make sure all required heat treating occurs after equipment maintenance. 410SS and similar ferritic stainless steels have limited availability. They are most often seen as vessel linings and sheet and plate for vessel internals. While they can be procured in piping, delivery times are often long. They are generally more resistant to chloride stress corrosion cracking and may be a choice for services that preheat crude upstream of the desalter with high temperature rundown streams. 304SS, or other 18-8 austenitic stainless steels, weld easily and have high resistance to sulfidation attack. However, they are susceptible to chloride stress corrosion cracking and should not be exposed to chloride-containing water. They are also susceptible to polythionic stress corrosion cracking if they are sensitized by exposure to high temperatures (above 425°C to 455°C, 800°F to 850°F). Type 304SS, 316SS, 317SS, 321SS, and 347SS all have essentially the same resistance to sulfidation. If sulfidation is the concern, the cost differential of the other types above 304SS is rarely justified. L-grades such as 304L are typically specified in order to meet welding requirements. 2

Rio Oil & Gas Expo and Conference 2012 Under high temperature conditions, coke formation on fired heater tubes can protect the metal surface by insulating the metal from the sulfur in the flowing fluid. It is recommended that this fact never be used by itself to justify selecting carbon steel instead of 5-Cr or 5-Cr instead of 9-Cr tubes for fired heaters. 2.2 Operating Condition Limits Little room is available for operating condition limits to alleviate sulfidation corrosion. The oil has to get hot to recover distillate. Lower velocities will help reduce corrosion rates. For this reason, good practice avoids vaporization in the preheat train, which creates high velocities in piping and equipment. 2.3 Feed Quality Control It is possible to blend crudes together to lower sulfur contents. This is a viable technical method for sulfidation corrosion control. However, for a new unit, upgrading metallurgy to handle cheaper, higher sulfur crude is usually attractive. 2.4 Chemical Additives Additives have not proven cost effective for sulfidation corrosion prevention on a continuous basis. They have been used for situations where intermittent and short periods of high-sulfur crudes have been run. The benefits of additives are unclear. 2.5 Preventive Maintenance and Inspection Preventive maintenance and inspection plays a vital role in sulfidation corrosion monitoring. Sulfidation corrosion is usually general attack with some accelerated rates in local areas of high-temperature or high-velocity. PMI inspection for metal thickness has been effective for preserving crude unit integrity. PMI inspection programs should be included as appropriate as a function of operating conditions, feed qualities, and materials of construction.

3. Naphthenic Acid
Naphthenic acid corrosion varies greatly with the same nominal acid content in different crudes. While prediction is complex and uncertain, the solutions are simple. Three major solutions are available  Crude blending has had good historical performance in reducing naphthenic acid corrosion rates  Additives have recently demonstrated success in suppressing acid corrosion.  High-molybdenum alloys have proven resistance to naphthenic acid attack. The most common test methods for organic acid report a TAN (total acid number) for the crude. The TAN number does not distinguish between acid gas content (hydrogen sulfide), naphthenic acids, other organic acids, or acidic other contaminants. For the same acidity reading, different naphthenic acids also have different corrosion rates and different corrosion versus temperature profiles. The acid species also appear to interact with each other. In laboratory tests, mixtures of acid blends have been shown to have dramatically different corrosion rates from the pure acids. Combining these factors results in different crudes having dramatically different corrosion behavior for the same TAN value. For a specific crude, characteristics generally lie within a narrow range. If experience with a specific crude shows either a high corrosion rate or a low corrosion rate, future deliveries of that crude are very likely to have similar characteristics. Many cases of low-acid crudes with high corrosion rates have been reported (Nuget & Dobis 1998). Equally, many crudes with high acid numbers have shown low corrosion activity. The generally accepted difference between a high-acid crude and a low-acid crude is a TAN of 0.5. For products, the difference between a high-acid oil and a low-acid oil is a TAN of 1.5. However, these values are often disputed by individuals, plants, and companies. Most experience has shown that TAN values less than 0.5 for crude and 1.5 for products cause relatively little acid corrosion. For low-acid crude slates with plants on a regular turn-around cycle (4 years or less between inspection periods), extra upgrades for naphthenic acid protection are not normally done. Extensive experience shows that the temperature ranges where naphthenic acid corrosion has occurred vary from 204°C to 370°C (400°F to 700°F) (Derungs 1956). Corrosion can occur anywhere from the atmospheric column diesel draw section down through the vacuum heater, vacuum transfer line, and the vacuum tower from the LVGO pumparound section down. The most common locations are the vacuum tower HVGO pumparound section, vacuum tower wash section, vacuum tower transfer line, and, to a lesser degree, the vacuum charge heater. Areas subject to the most corrosion are those with high velocity and where vapor condensation occurs. The generic corrosion product of naphthenic acid is an iron naphthenate. Iron naphthenates are soft materials; they erode easily in situations where shear forces are applied. Naphthenic acid corrosion may be dramatically higher in 3

Rio Oil & Gas Expo and Conference 2012 high velocity areas, two phase zones, elbows, and other pipe fittings (Craig 1996). 3.1 Materials Selection Molybdenum contributes key resistance qualities that protect against naphthenic acid corrosion. While the chrome alloys, 410 SS, and 304SS normally have lower corrosion rates from naphthenic acid than carbon steel (Heler 1963), they do not meet contemporary requirements for processing acidic crudes. Table 2 lists typical compositions for some alloys commonly used when materials upgrades are made to resist naphthenic acid corrosion. The composition values here are for ‘typical’ composition based on the lower quartile of the allowable range in composition for the alloy. 316L is considered the minimum grade that protects against naphthenic acid corrosion (Piehl 1987). Extensive work has taken place to quantify the value of molybdenum. However, laboratory work has consistently failed to replicate the effect of molybdenum seen in the plant. Most laboratory data show little, if any, consistent benefit from molybdenum (Gutzeit 1976, Babain-Kibala et al. 1993, Craig 1995). Many rules of thumb have been proposed. These are all based on plant experience. Take care to understand the context of the operating conditions that these rules are based on (Tebbal & Kane 1998) before applying them. Table 2. Materials Composition – Typical Naphthenic Acid Resistant Materials UNS Trade Forms Composition (weight percent) Nominal Cr Ni Mo Cu N2 18.3 9.0 0.08 16.4 10.2 2.1 0.05 18 11.6 3.1 0.05 21 25 4.5 1.6 20.5 24 6.3 0.1 0.22 15.5 57 15.5

C S30403 304L 0.02 S31603 316L 0.02 S31703 317L 0.02 N08904 904L 0.02 N08367 AL-6XN® 0.02 N10276 C-276® 0.005 Ref: Rolled Alloys 2009, Ellis 1998



Mn 1.7 1.6 1.5 1.7 0.3 0.5

3.1.1 Crudes with a TAN below 0.5 Few incidents of naphthenic acid corrosion by crudes with a TAN of 0.5 or below have been reported. The chrome alloys, 410SS, and 304SS often provide the minimal protection required to run many of these crudes. Conventional PMI required to monitor sulfur induced corrosion will usually suffice. As experience accumulates on a specific crude, some upgrades may be required. 3.1.2 Crudes with a TAN of 0.5 to 1.5 Based on the current market average of 2.1-2.2 weight percent molybdenum, 316L SS is typically suitable for processing crudes with a TAN number of up to ~1.5. It should be used from the vacuum heater outlet through the bottom of the LVGO section in the vacuum tower. This includes transfer line, cladding for the vacuum tower interior, vacuum tower internals, and the hotter (normally the first) exchangers on the HVGO pumparound exposed to hot HVGO. 316L SS cladding on the bottom of the atmospheric column vessel (area exposed to 316°C, 600°F) may be considered, but is not common. Vessel internals, piping and exchangers attached to the atmospheric column do not normally require upgrades for naphthenic acid at these levels. Velocities are normally low enough in the exterior equipment that corrosion rates are low. 3.1.3 Crudes with a TAN of 1.5 to 3.5 Based on a minimum molybdenum content of 3.1 weight percent, 317 SS is typically suitable for processing crudes with a TAN number of up to ~3.5. It should be used from the vacuum heater outlet through the bottom of the LVGO section in the vacuum tower. This includes transfer line, cladding for the vacuum tower interior, vacuum tower internals, and the hotter (normally the first) exchangers on the HVGO pumparound exposed to hot HVGO. 316L SS or 317L SS cladding on the bottom of the atmospheric column vessel (area exposed to 316°C, 600°F) should be included. For vessel internals, piping and exchangers attached to the atmospheric column 316L SS is normally sufficient. Again, this is due to the lower velocities. 3.1.4 Crudes with a TAN above 3.5 Crudes with a TAN above 3.5 often require considerable upgrading. The next step up in molybdenum content is 904L at 4.5 weight percent. However, 904L is a much more difficult material to obtain. The cost to going up to a higher grade alloy than 904L, but that one that is commonly available, is usually small. One alternate often mentioned is 4

Rio Oil & Gas Expo and Conference 2012 austenitic-ferritic duplex stainless steels, such as proprietary AL6-XN®. 904L and other high-Mo stainless steels also have operating temperature limits resulting from sigma-phase transformation (API RP571). For this reason, heater tubes should not be made from 904L or high-Mo alloys (duplex stainless steels). 904L may be used for vacuum tower transfer lines. One recommended approach is to use a carbon steel transfer line with a two-pass weld overlay of 904L. This preserves the base layer to protect against exterior chloride attack and uses the 904L as a corrosion resistant-only layer against inside attack from naphthenic acid. Due to the possibility of aggressive corrosion, proprietary alloys such as Hastelloy® C-276 have been used. Hastelloy® C-276 is essentially impervious to naphthenic acid attack. Due to its expense and softness, use of C-276 has been restricted to vessel cladding, pipe cladding, and vessel internals. Unless documented operating experience is available to support less expensive metallurgy, the following, or better, should be used for units processing crudes with a TAN above 3.5:  Atmospheric tower sections above 205°C (400°F): 316L SS clad and internals.  Atmospheric tower sections above 370°C (700°F): 317L SS clad and internals.  Atmospheric tower sidestrippers above 260°C (500°F): 316L SS clad and internals.  Atmospheric tower pumparound loops and product streams above 260°C (500°F): 316L SS clad equipment; 316L SS tubes and piping.  Atmospheric tower piping to vacuum system (hot vacuum tower feed): 317L SS.  Vacuum heater coil: 9-Cr.  Vacuum transfer line: 317L or 904L clad.  Vacuum tower sections above 177° C (350°F): 316L SS clad and internals.  Vacuum tower sections above 232°C (450°F): 317L SS clad and internals.  Vacuum tower sections above 288° C (550°F): Hastelloy® C-276 internals; 317L SS major support beams with 3 mm (0.125”) corrosion allowance; 317L SS clad vessel with 6.4 mm (0.25”) corrosion allowance. As a note, Canadian synthetic tar sands crudes, even though they may have high TAN values, have experienced relatively low naphthenic acid corrosion rates. Based on experience to date, the maximum metallurgy levels for them should be as shown for crudes with a TAN value of 2.5 or less. In contrast, Venezuelan heavy oil crudes have shown aggressive naphthenic acid corrosion. Metallurgical choices for the Venezuelan crudes should be conservative and include all applicable upgrades. 3.2 Operating Condition Limits Little room is available for operating condition limits to alleviate naphthenic acid corrosion. The oil has to get hot to recover distillate. Lower velocities will help reduce corrosion rates. 3.3 Feed Quality Control Considerable success has been seen with blending crudes to alleviate naphthenic acid corrosion. Many factors contribute to the success of crude blending. Reducing the concentration of naphthenic acids appears to be successful in reducing corrosion rates. In particular, getting the TAN values below 0.5 has shown great success. Sulfur has been shown to help prevent naphthenic acid corrosion (Dettman et al. 2009). Reactions of hydrogen sulfide with the metal form a resistant film that reduces naphthenic acid corrosion rates. Blending a high-sulfur crude with a high-naphthenic acid crude has been shown to significantly reduce naphthenic acid corrosion rates. Once the sulfur content of a feed blend reaches approximately five weight percent, the benefit stops and may even reverse. 3.4 Chemical Additives Recent work in phosphorous-based anti-corrosion agents has achieved significant success in specific cases (Zetlmeisl 1996, Rechtien 2006, Haynes 2006). This should be evaluated on a case-by-case basis and no credit should be claimed until definite data are available for a specific crude feed. 3.5 Preventive Maintenance and Inspection Corrosion can be seen as either general corrosion or as significant pockets of localized corrosion. Localized corrosion often occurs in regions of condensation (Tebbal 1999) or high-velocity two phase flow. These locations include the tower wall above pumparound returns, tower packing, and transfer lines. Depending upon metallurgy in place, PMI inspection for metal thickness should be maintained in these areas.

4. Chlorides
Heavy oil processing problems with chlorides are not new problems. Rather, they are a continuation of old problems, but under more severe conditions (Kronenberger 1984). Chlorides enter the crude unit as a component of 5

Rio Oil & Gas Expo and Conference 2012 dissolved salts in water mixed with the crude oil. The dissolved salts include sodium chloride, magnesium chloride, and calcium chloride. The crude unit desalter uses electrostatic precipitation to extract most of the water and reduce the chloride content of the crude. However, some chloride contamination passes the desalter and gets to the atmospheric heater. Upstream of the desalter, the chloride concentration is low enough, the water content is low enough, and the temperature is low enough that chloride corrosion rates are low. Carbon steel is an adequate choice for this part of the plant. The chlorides themselves are not the problem. At 175°C to 205°C (350°F to 400°F) the calcium chloride and magnesium chloride thermally decompose into the metal ion and chlorine. Chlorine rapidly reacts with hydrocarbons; and produces hydrogen chloride. At normal crude atmospheric heater operating conditions nearly all of the magnesium chloride and much of the calcium chloride will hydrolyze. Hydrogen chloride, in the absence of water, does not significantly corrode carbon steel. The overhead system of the crude tower will condense water. With water present, the water absorbs the hydrogen chloride and creates hydrochloric acid. At this point, many outcomes become possible. One key point is the location of where the first drop of water occurs. The first drop of water will occur at the point where film temperatures reach the dew point. Bulk temperatures are often reviewed, but this will miss many problems. Surface temperatures are what count. The initial drop of water may have very high hydrogen chloride concentrations; making it extremely corrosive. The water also absorbs ammonia. Hydrogen chloride combines with ammonia and form ammonium chloride. In situations where the water revaporizes, solid deposits of ammonium chloride form. The deposits can create the potential for under-deposit corrosion. If ammonia concentrations are high, ammonium chloride can precipitate directly from the vapor phase to a solid phase (Carlton 1963, Wu 1994). This can occur inside the atmospheric column (most common), overhead lines, overhead exchangers, or even in the vacuum column. The ammonium chloride then absorbs moisture, and starts the process of under-deposit corrosion. Common methods of alleviating chloride corrosion include additives; unit design; selection of operating conditions; corrosion inhibitors; and materials selection. Other strategies include using water wash to make sure that the initial water location is controlled and the corrosive species are quickly diluted. Putting all these factors together creates so much complexity that the 85 pages long NACE (National Association of Corrosion Engineers) Publication 34109 ‘Crude Distillation Unit – Distillation Tower Overhead System Corrosion’ barely counts as a brief introduction to the subject. 4.1 Evaluation of Existing Crude Units For evaluation of an existing crude unit, attention must be paid to identifying the following locations:  Areas susceptible to solid salt deposition.  Areas where water condensation starts.  Areas where water may revaporize. For each of these situations, a selection of materials upgrades and active measures need to be implemented. 4.2 Criteria for New Crude Units In spite of recurring pressure to improve heat recovery, the most important recommendation to reduce chloride corrosion is to not heat integrate the overhead system with the crude preheat train. This step allows for using generous rates of water wash in the overhead system, which dilutes the concentration of chlorides at the initial condensation point. Water wash also keeps the overhead system wet. This prevents solid deposits from forming. Without solid deposits, under-deposit corrosion cannot occur. (Giesbrecht et al. 2002, Whitehead & Ramachandran 1991). The author’s survey of crude units currently operating shows ~70% have heat integration between the overhead and the crude preheat. Crude overhead-to-feed heat integration is a relic of a bygone era. With low density crude, making high yields of naphtha, without preflash drums or towers, and short run durations (often 12-18 months) between shutdowns – these systems can work. In plants running difficult to desalt crudes, with preflash expansions, lower naphtha yields, and runs of 4 to 5 years – the crude-overhead-to-preheat is a major and continual problem. A well heat integrated unit can recover all the necessary preheat without the overhead heat integration service. Crude overhead-to-feed preheat should only be used on new units in exceptional cases. 4.3 Materials Selection The relevant corrosion mechanisms in this service are chloride induced pitting corrosion, crevice corrosion and stress corrosion cracking. Pitting corrosion is a localized corrosion mechanism present both when corrosive water is present and in under-deposit corrosion. Stress corrosion cracking occurs mostly in exposure of austenitic stainless steels to chlorides. Materials selection is not an exact science. Suitability of materials must be judged in the context of original cost; cost of repairs, both indirect and direct; expected life; preventive maintenance and inspection practices expected; 6

Rio Oil & Gas Expo and Conference 2012 and means of controlling process chemistry and conditions (operating conditions and additives). Additionally, apparently minor changes in fabrication practices, maintenance, and system chemistry can have major consequences. In general:  Downstream of the water wash addition point, carbon steel with an appropriate PMI program and chemical additives will meet requirements.  Based on the process configuration, a clad overhead line from the tower to the condensers may be required. Cladding should be either Monel® 400 or Hastelloy® C-276.  The top of the atmospheric column should be upgraded to a Monel® 400 or other chloride resistant cladding. Upgrading should be used down to two trays below any pumparound return temperature location below 120°C (250°F). Trays should also be upgraded to chloride resistant metallurgy.  In most units, caustic addition should be used downstream of the desalter to control hydrogen chloride generation. [See section on chemical additives.] 4.3.1 Selection Philosophy Carbon steel has a relatively low cost. For overhead exchangers, carbon steel should be the material of choice if two performance criteria can be met:  Exchanger bundle life reaches a minimum of four years.  The unit can reach the planned run length without a unit shut-down. Under these conditions, water wash, chemical additives, and normal PMI practices coupled with carbon steel is the most economic choice. Due to the cost of PMI and the difficulty of replacement, carbon steel must have an expected life of 10 years or more before it is the economic choice for overhead lines. Keeping the lines well-insulated to avoid water condensation due to surface heat loss is also a very cost effective means of reducing corrosion. Atmospheric tower cladding in the top section is nearly always required. If the conditions will permit it to last 15 years or more, Monel® is typically the best economic choice. If conditions are more severe, alloys such as C-276® are recommended. Monel® is usually the recommended choice for the top trays or packing in the atmospheric column (or preflash column) if the expected life is longer than four years and the unit can reach the planned run length without a shutdown. If damaged tray performance will cause a unit shutdown or serious economic consequences, more resistant materials should be used. 4.3.1 Stainless and Nickel-Based Alloys The main selection criteria used should be documented evidence of service in similar situations as well as the commonly accepted pitting resistance equivalent number (PREN) values. In general, the overhead systems chloride corrosion problems come from pitting corrosion, crevice corrosion, or stress cracking corrosion. Stress cracking corrosion is catastrophic failure. Materials subject to this failure should not be used. This includes the common austenitic stainless steels (304/L, 316/L and 317/L). One of the most common comparisons for pitting corrosion resistance is to compare PREN values which are calculated from the alloy composition. The key elements considered are chromium, molybdenum and nitrogen. Multiple formulas have been proposed for PREN calculation. These may include tungsten, copper, manganese and other elements (Bauernfeind & Mori 2003). The form used here calculates a PRENW value that includes tungsten (W). With the composition values in weight percent the equation is: PRENW = Cr + 3.3Mo + 16N + 1.65W (1)

The 304L, 316L, and 317L, materials have been added for comparison only. They are not proposed for use in chloride containing overhead systems. While Alloy 2205 is the most commonly used duplex alloy for marine environments (Davison & Redmond 1990, Allegheny Ludlum 1998) and has often been used for overhead exchanger tubing, it should be considered as the minimum upgrade for a crude unit overhead system if upgrades from carbon steel are required. Table 3 shows PRENW values compiled by Ellis (1998) based on a ‘typical’ composition set at the first quartile of the composition range. A variation in PRENW values of 4.0 or more should be expected to significantly change performance. All the upgrade choices shown have more than a 4.0 variation in PRENW between the maximum possible and the typical values. Crevice corrosion resistance typically requires material with a higher PRENW number. If history on a material shows that it resists pitting corrosion but is failing from crevice corrosion, approximately a 4.0 PRENW number increase will often resolve the crevice corrosion problem (Avery et al. 1996).


Rio Oil & Gas Expo and Conference 2012 Based on the PRENW values, enhanced materials can be grouped into three upgrade groups; a low, middle, and a high corrosion resistance. The low group includes materials with a PRENW range of 34-44. The middle group covers the range 45-56. The high group has PRENW values of 60 and higher. The low group includes 254MSO® as well as Alloy 255, and Alloy 2507. These have shown significant success. However, they have still had reduced life in specific cases. The medium group includes AL-6XN®, 654SMO®, Alloy B66, and Alloy 625. These materials mainly benefit over the low group by increasing nitrogen content and pushing the molybdenum content higher as well as adding tungsten in some alloys. This group of materials includes what are commonly referred to as the 6-Moly alloys. These alloys are suitable for all applications where chloride resistance is called for in the crude unit. Only a few problems have been reported with these materials. Table 3. PRENW summary of candidate metallic materials UNS Trade Forms Composition (weight percent) Nominal Ni Mo Cu N2 PRENW+ Typical Min Typ Max 18.5 23.9 29.2 32.3 34.0 37.3 40.2 42.9 43.0 50.3 51.8* 56.0 66.7 70.0 73.7 75.8* 87.2* 20.0 27.9 33.2 37.8 39.5 43.9 47.6 48.7 45.5 56.0

C Cr W Mn Not recommended S30403 304L 0.02 18.3 9.0 0.08 1.7 18.0 S31603 316L 0.02 16.4 10.2 2.1 0.05 1.6 22.6 S31703 317L 0.02 18 11.6 3.1 0.05 1.5 27.9 Low group upgrades: extended life in many situations, but still reported problems in other cases S31803 ATI 2205™ 0.02 22 5.6 3.0 0.14 1.5 30.5 N08904 904L 0.02 21 25 4.5 1.6 1.7 32.2 S32550 ATI 255™ 0.02 25.5 5.7 3.1 1.8 0.17 0.8 35.2 S32750 SAF 2507® 0.02 25 7.0 4.0 0.3 0.1 37.7 Middle upgrades: resistant to all except extreme cases N08367 AL-6XN® 0.02 20.5 24 6.3 0.1 0.22 0.3 41.2 S31254 254SMO® 0.02 20 18 6.1 0.7 0.20 0.7 42.2 N06625 Alloy 625 0.05 21.5 61 9.0 0.1 46.4 S31266 Alloy B66 0.02 24.5 22 5.1 1.5 0.45 2.0 3.0 URB66® S32654 654SMO® 0.01 24 22 7.3 0.5 0.5 3.0 54.3 High group upgrades: essentially no corrosion from chlorides in this service N06022 C-22® 0.003 21 57 13 3.0 0.3 64. N10276 C-276® 0.005 15.5 57 15.5 4.0 0.5 67.5 N06200 C-2000® 0.003 23 58.5 16 1.6 0.2 71.5 N06059 Alloy 59 0.005 23 59 16 0.4 Nicofer® 59 N10624 Alloy B-10 0.005 8.0 62 24 0.5 Nimofer® 6224 + Based on typical composition. * Based on nominal composition. Ref: Rolled Alloys 2009, Ellis 1998

61.2 74.4 77.8 80.1

The high group includes Ni-Cr-Mo alloys. This includes C-2000®, C-276®, C-22®, Nicofer® 59 and Nimofer® 6224. Under the conditions in crude overhead system most alloys in this group have very low to zero corrosion rates. Expected life exceeds 20 years in for all components (vessel cladding, tubes). While not perfect, C276® is the material likely to give the ‘best’ economic balance between mechanical properties, life, fewest corrosion problems, and cost. For crude unit operation, C-276® is nearly impervious to chloride corrosion. 4.3.2 Copper Alloys One commonly used material not listed in Table 3, Monel® 400, is a nickel-copper alloy. The performance of Monel® 400 lies between the low-resistance and medium-resistance group. Monel® 400 has a typical composition of 66-Ni, 31-Cu, 1.0-Mn (plus minor components). For many years Monel® 400 has been considered the basic chlorideresistant material. However, as run-length between shutdowns has increased, more resistant alloys have been investigated. 4.3.3 Titanium Alloys Due to difficulty in fabrication, titanium is not recommended for vessel or exchanger linings. However, it is an excellent choice for exchanger tubes. Most grades of titanium have excellent corrosion resistance in overhead systems. 8

Rio Oil & Gas Expo and Conference 2012 Titanium Grades 7 through 12 all have good chloride corrosion resistance (Kirby 1985). Grade 7 has been considered the most chloride-corrosion resistant of the grades (Kirby 1995). However, the cheaper Grade 16 and Grade 38 will also meet the requirements for most units. 4.4 Operating Condition Limits The critical point in corrosion from chlorides is the initial point of water condensation. Water condensation is driven by surface temperatures rather than bulk temperatures. It is very difficult to measure surface temperatures so bulk temperatures are typically measured. Common practice often adds a temperature control to the overhead of crude columns and preflash columns. The intent of this control is to prevent water condensation in the column. Typical practice sets a tower overhead temperature 17°C to 28°C (30°F to 50°F) hotter than the calculated dew point. Shock condensation occurs when cold reflux enters the tower and creates localized water condensation. This is a common mechanism for corrosion inside the tower. Operating at maximum reflux rates allows an increased reflux return temperature for the same heat removal. Within the constraints of tower and external equipment, reflux and pumparound rates should be maximized. 4.5 Feed Quality Control Feed quality can help reduce chlorides overhead. Major steps possible include running lighter crudes (improves desalter operations) and using cleaner desalter water. The key element for the desalter water is to keep ammonia content below 100 wpmm, hydrogen sulfide as low as possible and water pH in the range of 6.5-7.5. 4.6 Chemical Additives Chemical additives have made significant progress in the last 20 years in mitigating chloride corrosion. The major chemical vendors should be consulted as needed. No chemical addition program will completely eliminate corrosion. Optimally, chemical additives should change with the crude type or blend. No specific recommendations for chemical additives are made here as they will strongly depend upon the supplier, crude processed, and specific unit constraints. Based on the author’s surveys, more than 65% of plants use caustic injection into the crude. The injection occurs downstream of the desalter. The intent of caustic injection is to react magnesium chlorides and calcium chlorides with the caustic to create sodium chlorides (Scherrer and Baumann 1982). For the most part, sodium chlorides are heat stable at atmospheric heater operating conditions. Some limited sodium chloride breakdown occurs in many vacuum heaters. Sodium is a known coke promoting agent. As long as total sodium content in the atmospheric tower feed is less than 24 weight ppm, coking rates are usually low. 4.7 Preventive Maintenance and Inspection PMI includes both monitoring of metal thickness and monitoring overhead water quality. One common method, measuring iron content in the overhead water, is routinely used as a monitoring tool. Coupons are less successful in monitoring corrosion rates with many located in elbows or other fittings. Localized flow patterns in the fittings often lead to inaccurate conclusions. Coupons are also installed in a limited number of locations.

5.0 Disclaimer
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6.0 References
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Rio Oil & Gas Expo and Conference 2012 BAUERNFEIND, D., AND MORI, G. Corrosion of superaustenitic stainless steels in chloride- and sulfate-containing media - influence of alloying elements Cr, Mo, N, and Cu. NACE 03257, Corrosion 2003. San Diego: NACE, Houston, TX, 16-20 March, 2003. CARLTON, R. H. Refinery condenser and exchanger corrosion by ammonium chloride. Materials Protection: 15-20, January, 1963. CRAIG, H. L., JR. Naphthenic acid corrosion in the refinery. NACE 95333, Corrosion 1995. Orlando, FL, 26-31 March, 1995. CRAIG, H. L., JR. Temperature and velocity effects in naphthenic acid corrosion. NACE 96603, Corrosion 1996. Denver: NACE, Houston, TX, 24-29 March, 1996. DAVISON, R. M., AND REDMOND, J. D. Practical guide to using duplex stainless steels. Materials Performance 29: 5862, Jan, 1990Technical Marketing Resources Inc. Materials Selection & Design. DERUNGS, W. A. Naphthenic acid corrosion - an old enemy of the petroleum industry. Corrosion 12 (12): 41-46, Dec, 1956. DETTMAN, H., LI, N., AND LUO, J. Refinery corrosion, organic acid structure, and Athabasca bitumen. NACE 09336, Corrosion 2009. Atlanta: NACE, Houston, TX, 22-26 March, 2009. ELLIS, P. F. Quantitative tool for FGD alloy selection based on pH and chloride. NACE 98483, Corrosion 1998. San Diego: NACE, Houston, TX, 22-27 March, 1998. GIESBRECHT, W., DUGGAN, G., AND JACKSON, D. Effective corrosion control techniques for crude unit overheads. NACE 02477, Corrosion 2002. Denver: NACE, Houston, TX, 7-11 April, 2002. GUTZEIT, J. High temperature sulfidic corrosion of steels. In: Process Industries Corrosion, edited by B. J. Moniz. NACE, Houston, TX, 1986. GUTZEIT, J. Naphthenic acid corrosion. NACE 76156, Corrosion 1976. Houston: NACE, Houston, TX, 22-26 March, 1976. HAYNES, D. Naphthenic acid bearing refinery feedstocks and corrosion abatement., AIChE Chicago Symposium. Chicago, 9-10 October, 2006. HELER, J. J. Corrosion of refinery equipment by naphthenic acid. Materials Protection 2 (9): 90-96, Sept, 1963. KIRBY, G. N. Fight chloride corrosion in aqueous systems. Chem Eng Prog: 47-53, February, 1995. KIRBY, G. N. Selecting alloys for chloride service - Part 2. Chem Eng, March 4, 1985. KRONENBERGER, D. L. Corrosion problems associated with the desalting difficulties of Maya and other heavy crudes. NACE 84128, Corrosion 1984. New Orleans: NACE, Houston, TX, 2-6 April, 1984. MCCONOMY, H. F. High temperature sulfidic corrosion in hydrogen-free environment. In: Proceedings API Division of Refining. API, 1963, Vol. 43 (III), p. 78-96. NACE. Crude Distillation Unit - Distillation Tower Overhead System Corrosion. (NACE), 34109. Houston: NACE, Houston, TX, 2009. (85). NACE. Effect of Nonextractable Chlorides on Refinery Corrosion and Fouling., 34105. Houston: NACE, Houston, TX, 2005. (16). NUGENT, M. J., AND DOBIS, J. D. Experience with naphthenic acid corrosion in low TAN crudes. NACE 98577, Corrosion 1998. San Diego: NACE, Houston, TX, 22-27 March, 1998. PIEHL, R. L. Naphthenic acid corrosion in crude distillation units. NACE 87196, Corrosion 1987. San Francisco: NACE, Houston, TX, 9-13 March, 1987. RECHTIEN, R. Naphthenic acid corrosion control strategies., AIChE Chicago Symposium. Chicago, 9-10 October, 2006. ROLLED ALLOYS. Bulletin 1048, 2009. SCHERRER, C. J., AND BAUMANN, C. R. Update of the desalted crude neutralization process. NACE 82101, Corrosion 1982. Houston: NACE, Houston, TX, 22-26 March, 1982. SLAVCHEVA, E., SHONE, B., AND TURNBULL, A. Factors controlling naphthenic acid corrosion. NACE 98579, Corrosion 1998. San Diego: NACE, Houston, TX, 22-27 March, 1998. TEBBAL, S. Critical review of naphthenic acid corrosion. NACE 99380, Corrosion 1999. San Antonio: NACE, Houston, TX, 25-30 April, 1999. TEBBAL, S., AND KANE, R. D. Assessment of crude oil corrosivity. NACE 98578, Corrosion 1998. San Diego: NACE, Houston, TX, 22-27 March, 1998. WHITEHEAD, T. D., AND RAMACHANDRAN, P. A. An analysis of water wash practices used for corrosion control in condensible hydrocarbon systems. NACE 91318, Corrosion 1991. Cincinnati, OH: NACE, Houston, TX, 1115 March, 1991. WU, Y.-M. Calculations estimate process stream depositions. Oil & Gas Journal 92 (1): 38-41, 3 January, 1994. ZETLMEISL, M. J. Naphthenic acid corrosion and its control. NACE 96218, Corrosion 1996. Denver: NACE, Houston, TX, 24-29 March, 1996.