Case Studies and Best Practices of Refinery Caustic Injection Systems

Authors: Ahmad S. Al-Omari, Ahmed M. Al-Zahrani, Dr. Graham R. Lobley, Dr. Robin D. Tems and Olavo C. Dias

Caustic injection is used to reduce refinery crude-column overhead hydrochloric acid (HCl) corrosion. Such injection systems are considered to be critical equipment because failures can potentially have catastrophic results. Accordingly, it is necessary to rigorously design caustic injection systems to assure correctness and reliable performance. Two case studies are presented to demonstrate the advantages and disadvantages of different designs and materials that have been used. Failures encountered in caustic injection systems are also discussed. This article draws on refinery experience to provide a comprehensive approach to design and operation. Keywords: caustic injection, caustic stress corrosion cracking, NaOH, quill

Corrosion in refinery crude units is a common problem worldwide. The principal agent causing overhead corrosion is hydrochloric acid (HCl), although amine chlorides, hydrogen sulfide, organic acids, sulfur oxy-acids, and carbon dioxide can also contribute to overhead corrosion. Oxygen, introduced through poorly managed water wash systems, can make corrosion worse. Hydrochloric acid induced overhead corrosion is primarily controlled by chloride management in the incoming crude oil and secondarily controlled by the use of a supplemental injection of organic neutralizers and corrosion inhibitors in the overhead system. Chloride management consists of good crude tank handling, desalting, and then polishing/neutralizing with aqueous sodium hydroxide, which is commonly called caustic1. It is this injection of caustic which is the subject of the present article. Refinery crude feeds contain water and inorganic salts (sodium, magnesium and calcium chloride). Hydrolysis of calcium and magnesium chlorides (CaCl2 and MgCl2) occurs when crude oil is heated in the preheat exchangers and fired heaters. The hydrolysis of gaseous HCl is depicted in the following chemical reactions2: CaCl2 + 2H2O MgCl2 + 2H2O NaCl + H2O

Fired heater temperatures typically range from 680 ºF to 716 ºF (~360 ºC - 380 ºC). In this temperature range, sodium chloride is mostly stable, but most magnesium chlorides and between 20% to 50% of the calcium chlorides are hydrolyzed. Caustic is added to the crude charge, downstream of the desalter, to react with the calcium and magnesium chlorides, forming the more stable sodium chloride. Caustic also reacts with any HCl vapor produced. The reaction product, sodium chloride, is more stable at heater temperatures and accumulates in the distillation column bottoms, rather than the overhead system3. While aqueous caustic injected into the crude flow can be extremely beneficial, it can also be detrimental. Concentrated caustic solutions can cause general corrosion of carbon steel equipment at these temperatures. Additionally, caustic can cause caustic stress corrosion cracking (CSCC) of non-post weld heat treated carbon steel and of austenitic alloys including stainless steels and nickel alloys such as Alloy 825 (UNS N08825). If allowed to precipitate, caustic/salt reaction products (calcium and magnesium hydroxide) can cause plugging of heat exchanger tubes. Lastly, caustic can also contaminate catalyst beds downstream if present at higher levels in heavy side-cuts. This article identifies some key features of caustic injection quill installations and illustrates potential failure modes by examining two specific failures: the CSCC failure of an Alloy 825 caustic injection quill, and the general caustic corrosion failure of a carbon steel piping system caused by installation errors in an Alloy 400 (UNS N04400) injection quill.

Most refineries inject caustic into the crude feed to the crude unit distillation tower to control condensation of HCl downstream of the distillation tower in the overhead line. Caustic injection is carefully balanced with chloride levels measured in the overhead receiver. Typically, operators specify chloride levels to be between 10 ppm and 30 ppm. The lower limit is set to avoid over treatment with caustic. Over treatment with caustic can result in contamination of the heavy products from the crude distillation tower with sodium, which can affect downstream units such as cokers, visbreakers and Fluid Catalytic Cracking (FCC) Units. One best practice limits sodium to 25 ppm in the visbreaker feed.

➞ ➞ ➞

Ca(OH)2 + 2HCl > 250 ºF (~120 ºC) (1) Mg(OH)2 + 2HCl > 400 ºF (~205 ºC) (2) NaOH + HCl > 900 ºF (~480 ºC) (3)


“B” Caustic Injection


system, are all required to ensure that the system operates safely. Failure of the caustic injection quill at this location could result in catastrophic failure of the hot crude line.

Flash Drum Desalter “A” Caustic Injection

Secondary Preheat Exchangers Wash Water

“C” Caustic Injection

Fired Heater

Atmospheric Column

Crude Tank Primary Preheat Exchangers

Two cases of caustic injection quill failures are described in the following sections. These case studies have been selected to represent a wide variety of challenges that other refineries worldwide may face due to several factors including incorrect materials and improper design.
Case #1: Caustic Corrosion and Cracking on Alloy 825 Caustic Injection Quill

Fig. 1. Caustic injection locations in the crude line.

Injection of caustic may be performed at one or two locations in the crude unit. Figure 1 demonstrates different locations of caustic injection in the refinery crude unit. Caustic may be injected upstream of the desalters “A.” Additionally, it is always injected at a location between the desalter and the fired heaters “B” and “C.” The location of this second injection point varies from refinery to refinery. It may be injected immediately downstream of the desalter “B” or immediately upstream of the heaters “C.”
Injection Upstream of the Desalter “A”

Quill Material: Alloy 825 (UNS N08825) Process Parameter: 290 ºC (554 ºF) Time to Failure: 11 months Crude Unit Capacity: 400 MBD This refinery used to inject caustic downstream of the desalter, but due to severe fouling of the heat exchangers downstream of the desalter, the caustic injection was relocated to be upstream of the heater. A caustic injection quill made from Alloy 825 failed prematurely by caustic corrosion and cracking, when in contact with high temperature crude oil (290 ºC). Premature failure of the quill occurred after 11 months service. The location for caustic injection in the crude transfer line was upstream of the crude heater. Visual inspection showed significant wastage, especially at the outer diameter of the quill tip, where it was exposed to the

Caustic injection upstream of the desalter may be used for controlling the pH of the desalter brine. Overdosing caustic at the upstream of the desalter can promote emulsions in the desalter.
Injection Downstream of the Desalter “B”

Caustic injection downstream of the desalter is recognized as an effective method to reduce overhead corrosion. Caustic is usually injected at a low concentration, of the order of 1 to 5 weight percent (wt%) aqueous solution. This low concentration requires a greater volume that aids effective mixing with the crude stream. The injection of a low concentration also reduces the risk of caustic corrosion and CSCC. To minimize fouling of the heat exchangers, it is critical that caustic quality be strictly controlled. At refineries where there are large fluctuations in caustic quality, heat exchanger fouling has been a problem.
Injection Upstream of the Heater “C”

Caustic injection upstream of the crude heater is an alternative if heat exchangers downstream of the desalter experience severe fouling. At these higher temperatures there are increased risks from caustic injection. Therefore, within the industry, only about 20% of refineries have adopted this method of caustic injection. Caustic injection at this location involves much greater risk because the consequences of a high temperature process leak are far more severe and corrosion damage at these elevated temperatures tends to be rapid. The proper design, materials selection, and inspection of the

Fig. 2. Alloy 825 quill.

Case #2: Failure of Old Design Caustic Injection Quill Due to Extended Slot Effect

Quill Material: Alloy 400 (UNS N04400) Process Parameter: 290 ºC (554 ºF) Time to failure: 3 months Crude Unit Capacity: 400 MBD The old design of the caustic injection quill used an open-end quill with a beveled tip that was slotted, as shown in Fig. 4 (new designs employ a closed-end, side hole design). The concept for this design is that the crude stream pushes the caustic mixture through the slot in the quill, creating turbulence and mixing downstream. Moreover, this design restricts the caustic flow to the pipe centerline area promoting mixing and dilution prior to contacting the pipe wall. One refinery experienced a leak at the injection location after three months in service. A longitudinal slot of 9½” in the Alloy 400 quill exceeded the specified 3” slot, allowing caustic to reach the top surface of the crude line, causing localized caustic corrosion, Fig. 5. This quill is shown in Fig. 6. This failure shows that the injection of caustic should be within the center third of the pipe to avoid any immediate contact between the hot mixed crude/caustic and the pipe wall.

Fig. 3. Alloy 825 flange cracking, crack origin at tube side, x200.

These, and other case studies, show that caustic injection systems require proper design, material selection guidelines, and installation procedures. These best practices are necessary to ensure the safety and reliability of the caustic injection systems, especially at high temperature locations. The following guidelines were developed based on field experience with the caustic injection at five refineries.
Proper Design

Fig. 4. Open-end quill.

Fig. 5. Configuration of the failed quill that has a 91⁄2” longitudinal slot.

Injection of caustic requires a precision engineering design of the whole injection system. The quill should be designed to efficiently disperse injected chemicals into a process stream without allowing concentrated caustic to corrode interior walls of the pipe, and without clogging the injection quill opening. The injection quill should be capable of injecting the caustic solution in such a way as to effectively and intimately mix the caustic with the process stream. The injection quill must be sized to inject the desired amount of caustic. If the

highest temperatures within the stream, Fig. 2. The quill tube was welded to the flange without stress relief. Although this was a lower temperature exposure region (caustic premixed with crude slipstream around 200 ºC), significant transgranular stress corrosion cracking was also observed in both the tube and flange material, as shown in Fig. 3. In the present case, the quill was redesigned to have a closedend tip with a side hole and the material was replaced with Alloy 4004. Since then, the quill never experienced failure.

Fig. 6. The failed Alloy 400 quill due to slot extension.


Caustic Inlet

Crude Slipstream Inlet

45º - 60º Side View Front view

Fig. 7. Injection quill with open end: Not recommended for caustic injection.

Monel Reducing Nipple

Monel Static Mixer

Monel Blind Flange

Monel Quill

Side View

Front View

Pipe Flow

Fig. 8. Side hole opening quill design with the correct orientation.

crude unit throughput is changed, the caustic injection system must be reviewed to ensure that the system is capable of handling the new throughput. In general, there are two styles of the injection quill design which are open-ended that has an angled bevel cut, Fig. 7, and the closed-end with the side hole opening style, Fig. 8. The style of the caustic injection quill with a bevel cut open-end is not recommended. Based on the field experience, several failures due to the use of this type of quill have occurred, as shown in Case #2. The disadvantage of the quill with an angled open-end is that at low process stream flow rates, there tends to be a concentration of the injected caustic at the pipe wall surface below the injection point. This inhibits dilution of caustic by the main process stream, and allows exposure of the pipe wall to a concentrated caustic, thereby promoting localized corrosion. The preferred design of a caustic injection quill is one that directs the caustic flow downstream, such as the side hole quill, as shown in Fig. 8, with the opening oriented downstream. The caustic injection quill, as shown in Fig. 9, should not be fabricated using pipe with a welded end plate. Cracking around a circumferential fillet weld can occur, due to the difficulty of getting a sound weld in this restricted area.

Fig. 9. Caustic chemical injection point.

The caustic injection quill should be fabricated from solid Alloy 400 (UNS N04400) bar stock. The design, materials, fabrication, examination, and testing of the fabricated Alloy 400 bar should meet the requirements of American Society of Mechanical Engineers code (ASME) B31.3 “Process Piping.” Fabricating the caustic injection quill by boring a solid Alloy 400 bar is considered as unlisted components in ASME B31.3. ASME B31.3 defines unlisted components as components not listed in Tables 326.1, A326.1 or K326.15. The processes used to fabricate the caustic injection quill should be reviewed for ASME B31.3 code compliance. Some fabrication processes can cause gross or local wall thinning. The crucial first stage in the process of fabricating the caustic injection quill is to perform positive materials identification (PMI) on the bar material to assure that the material is indeed Alloy 400. The bar should be in the “annealed” condition,



which will give yield strength in the range 25 ksi to 50 ksi. Machining should be done in more than one step. First, a rough cut is required followed by fine cutting. The objective is to minimize work hardening the Alloy 400 surface. All machining should be performed with adequate lubrication. The quill should be examined in accordance with the ASME B31.3. Dimensions and mechanical properties of the fabricated quill must be compatible with the other components of the injection system, except as allowed by paragraphs 303 and 304 of ASME B31.3. The pressure/ temperature design of the fabricated caustic quill should provide the same safety margins as ASME B31.3. The caustic injection quill design should also be evaluated for potential fatigue cracking due to flow induced vibration. Process stream flow rate fluctuations, flow regimes, fluid viscosity and the quill’s natural frequency are all essential variables affecting injection quill design. Natural frequency and wake frequency calculations should be performed to determine the optimum injection quill insertion length for each quill that will be installed in the field. The purpose of these calculations is to prevent the quill from entering a resonant vibration condition in which fatigue failure can occur. The wake frequency should be less than 80% of the quill’s natural frequency to guarantee no resonant harmonic vibration.
Caustic and Crude Slipstream Injection

injection systems at five refineries, should be two to three times the velocity of the crude in the main stream line. The higher velocity at the orifice(s) results in a better mix. Caustic injection systems require continual operator attention to ensure that the correct dosage rate is being injected. Adjustments to the volume of caustic should be made to maintain the dosage rate set point. Installation of a flow meter on the caustic tank discharge lines is important in providing an accurate caustic dosage, instead of depending on the level of caustic tanks. Plant operators should check the caustic concentration and injection rates twice per shift. Operators should also visually check the condition of the caustic injection pumps, tanks and piping on a daily basis. Maintaining the optimum caustic dosage to process streams and monitoring the effect on corrosion rates are extremely important in corrosion control. Failure to do so would result in unwanted surprises and unplanned equipment failures.
Materials Selection

The proper design of the caustic injections system at a high temperature location should include6: • Premixing the dilute caustic stream with a crude slip stream. • Injection of the blended slipstream into the center third of the main crude line. • Sufficient velocity of the injection stream entering the main crude flow. Injecting caustic into high temperature crude streams is potentially risky. Injection of caustic into a lower temperature crude slip stream prior to injection into the main crude flow reduces the potential for caustic pooling and damage to the main line. It is very important to stop injecting caustic during slipstream crude flow interruptions, avoiding formation of concentrated caustic pools in the carbon steel system. It is, therefore, strongly recommended that a low-flow shutdown switch be installed to stop the caustic pump when the slipstream crude rate decreases to less than 85% of its design flow rate. To obtain proper mixing, it is essential to already have a homogenous mixture of caustic in the crude slipstream prior to the main process stream injection point. The most important consideration in the design of the crude slipstream is to establish a controlled flow that will maintain a high injection velocity into the main crude stream. The caustic injection and slipstream injection orifice velocities should be the same. Velocities of the crude slipstream, caustic and crude line, should be carefully measured and considered in the design of the injection system. The caustic and slipstream velocities at each orifice, derived from the experience in operating caustic

Several materials were used to fabricate the caustic injection quills at five refineries. Some of these quills were carbon steel, austenitic stainless steel, high nickel alloy and Alloy 400. Quills were in both low temperature and high temperature locations. Caustic can be used in contact with the austenitic types, up to moderate temperatures. But in strong solutions of caustic, at temperatures approaching boiling point, stress corrosion cracking can occur7, 8. Cracking of these materials may start a few days or weeks after installation. Nickel base alloys are more resistant to cracking and may be required at higher temperatures and/or caustic concentrations. Addition of nickel generally improves the resistance of steel to corrosion by alkaline solutions. The beneficial effect is most pronounced in hot and concentrated caustic solutions9. Handling caustic solutions at high temperatures requires higher alloys. Alloy 400, a nickel-copper alloy, is a reliable field-proven alloy for injection quills in refinery services. One caustic injection quill made from Alloy 400 was replaced after 15 years in service, validating Alloy 400 as a satisfactory material for caustic injection quills. Other highnickel alloys can also be used to handle hot caustic. For example, injection quills fabricated from Alloy 625 (UNS N06625) have been used by some refineries. Although, while Alloy 625 is reported to be practically unaffected by caustic, up to temperatures of 320 ºC, quills made from Alloy 825 have cracked due to CSCC of Alloy 825, as already shown in Case #1.

Caustic at elevated temperatures is extremely corrosive and can corrode the injection quill or the pipe wall itself if the quill is incorrectly positioned. The injection quill itself must be carefully aligned in the pipe where caustic will be injected. Caustic injection quills should be installed per approved design drawings and inspected to verify that the injection



Proper insertion depth should be within center third of pipe.

Fig. 10. Quill insertion limits.

quill is inserted to the proper depth during installation. The caustic injection quill should be inserted with the side hole opening within the center third of the pipe as shown in Fig. 10. This Figure illustrates a side view of the caustic injector installed in a piping section. Generally, the most effective position for caustic injection is at the center of the pipe. The highest fluid velocity is normally at the center of the line, therefore, injection at this point is intended to prevent concentration of the caustic at the edge where the velocity is low, due to friction, and will ensure efficient distribution of the caustic. It is imperative that the caustic solution is not directed at the piping wall where it could cause local rapid corrosion attack and wall perforation. Field verification of the pipe diameter and quill length must be confirmed by inspection and maintenance personnel prior to installation. The location of the quill tip should be confirmed after installation and before startup by radiography. Correct positioning of the quill is critical. The quill opening should be aligned parallel to the process flow with the quill opening points downstream when the injection tube assembly is placed in the process pipe. A match-mark indicator can be used to show the orientation of the quill opening.

Scans and Infrared Surveys. Most facilities now have inspection procedures that provide guidelines to plant personnel on the injection point’s identification, tracking and monitoring. Company policy now requires nondestructive testing (NDT) inspections every three months for newly installed caustic quills during the first year of operation. Radiography and thermography are two tools that can determine if the orientation of the quill opening is correct and if there are any signs of corrosion in the quills and/or flange connections. Moreover, all PMI performed during quill fabrication and installation should be documented and logged in the refinery inspection files. After installation and before startup, a radiograph must be taken to prove the quill tip location and orientation meets specified requirements. A permanent record must be kept by the Inspection Department. It is recommended that a digital photograph before installation be taken of the quill tube inserted in the pipe, so that the initial condition and details of the quill can be noted and compared to future in-service inspections. This photograph should be documented in inspection files. The refinery should have current as-built quill detailed design drawings that also specify the quill materials of construction. These drawings should be up-to-date and signed off.

Two case studies showing failures of caustic injection quills were discussed. These failures were related to problems in design and incorrect material selection. Operating experience in Middle Eastern refineries has demonstrated that Alloy 400 material performs well in crude unit caustic injection quills. Caustic injection quills must be carefully designed and installed to prevent caustic impingement on the pipe wall, otherwise critical failures can still occur. The concentration and dosage rate of caustic must be carefully controlled to avoid the caustic cracking of alloys. A well-designed caustic injection system, operated by experienced personnel (with full understanding of the consequence of any failure of this system) is an integral part of safe refinery operation.

Monitoring and inspection are key activities in the caustic injection system integrity. Inspection must be performed regularly, and must include the injection point itself, downstream and upstream piping, and associated equipment. Detailed inspection requirements are provided in API 570 “Piping Inspection Code Inspection, Repair, Alteration, and Rerating of In-Service Piping Systems.” It specifically highlights accelerated or localized corrosion from normal or abnormal operating conditions that require enhanced inspections10. Industry experience has shown that there have been unexpected failures at injection point locations when using traditional ultrasonic testing (UT) and radiographic testing (RT) techniques. Accordingly, companies are increasingly looking at more sophisticated techniques such as High Temperature UT

1. Rue, J.R. and Edmondson, J.G.: “Control of Salt-Initiated Corrosion in Crude Unit Overhead Systems,” Corrosion 2001, Paper 01538. 2. Alley, D.W. and Coble, N.D.: “Corrosion Inhibitors for Crude Distillation Columns,” Materials Performance, May 2003, pp. 44-49. 3. Bagdasarian, A., Feather, J., Hul, B., Stephenson, R. and Strong, R.: “Crude Unit Corrosion and Corrosion Control,” Corrosion 96, Paper 615.




4. Lobley, G.R., Buraiki, I.A., Kermad, A. and Nabulsi, K.M.: “Caustic Cracking: Incidents in Refineries,” Corrosion Control 2007, Paper 80, Sydney, Australia. 5. ASME B31.3, “Process Piping.” 6. Refinery Injection and Process Mixing Points, NACE International Task Group 174, Publication #3410, 2001. 7. Baboian, R.: “NACE Corrosion Engineer’s Reference Book,” 3rd edition, NACE International, 2002. 8. NACE International, Standard RP0403-2003, NACE International, 2003. 9. Roberge, P.R.: “Handbook of Corrosion Engineering,” McGraw-Hill, 2000. 10. API 570, “Piping Inspection Code Inspection, Repair, Alteration, and Rerating of In-Service Piping Systems.”

Ahmad S. Al-Omari is a Corrosion Engineer with 7 years of field experience working with Saudi Aramco since November 2001. He received his B.S. in Mechanical Engineering from King Fahd University of Petroleum and Minerals (KFUPM), Saudi Arabia, in 2001. Ahmad is currently working towards acquiring his master’s degree in the field of materials science. He was on assignment with the Consulting Services Department during the period of April 2006 to January 2008. Ahmad is now working with the North Ghawar Producing Department. He has performed several failure analyses in the areas of metallurgy and corrosion. Ahmed M. Al-Zahrani joined Saudi Aramco in 1995 with a B.S. degree in Chemical Engineering from King Fahd University of Petroleum and Minerals (KFUPM). Over the last 13 years, he worked with many Saudi Aramco departments such as the Process and Control System Department, Abqaiq Plant, Shedgum Gas Plant and Consulting Service Departments. In 2002, Ahmed received his M.S. degree in Materials Science and Engineering from Pennsylvania State University, PA. In 2005, he had a one year assignment with Chevron Technology Company, San Francisco, CA. Currently, Ahmed is Supervisor of the Corrosion Technology Unit of the Consulting Services Department. Also, he is the Vice Chairman of the International Association of Corrosion Engineers (NACE) Saudi Arabia Section. Ahmed has more than 13 technical publications in international conferences and magazines. Dr. Graham R. Lobley is a Consultant with the Materials Engineering Unit of the Consulting Services Department at Saudi Aramco. He has a Ph.D. in Metallurgy from Leeds University, UK and has written over 20 journal and international conference papers. Graham has 34 years’ professional work experience in the UK, USA and Saudi Arabia. His particular interests are in the fields of materials selection, engineering standards, failure analysis and equipment integrity, with emphasis on metallurgical damage mechanisms, environmental cracking and high temperature materials. Graham is a professional member of the Institute of Materials, Minerals & Mining, and a Chartered Engineer (UK).




Dr. Robin D. Tems is the Downstream Corrosion Team Leader and an Engineering Consultant in the Corrosion Technology Unit, Materials Engineering and Corrosion Control Division, Consulting Services Department. He holds a Ph.D. in Corrosion (1978), from the University of Newcastle upon Tyne, England. Robin is licensed as a professional member of the Institute of Materials, Minerals, and Mining (IOM3), as a Chartered Engineer (CEng), and as a Chartered Scientist (CSci) in the United Kingdom. Before joining Saudi Aramco in 1992, he worked for Mobil Research and Development Corporation in Dallas, Texas and Stavanger, Norway, focusing on corrosion and metallurgy in upstream operations worldwide. He has a long association with Saudi Aramco, serving as the Mobil team member to Shareholder Review Team No. 1 from 1982. Robin has over 33 years of professional experience and has over 50 publications on corrosion in the oil and gas and pollution control industries. He is a member of NACE International and is Vice Chairman of Technical Committee TG-108X. Previously, Robin served on the NACE Board of Director’s committee, chaired various symposia, and has chaired examination boards for the Engineering Council and Institute of Metallurgists. Olavo C. Dias is a Plant Integrity and Corrosion Consultant in the Consulting Services Department. Prior to joining Saudi Aramco in 2001, Olavo held key positions at major oil, gas and petrochemical companies, including ExxonMobil, Amoco and LyondellCitgo, both in corporate and field locations. He received his M.S. degree in Metallurgy from Pennsylvania State University, PA in 1977.




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