Stephen M. Patera, Sales Manager, LHI Metals. October 6-9, 2013 Caesars Palace, Las Vegas, Nevada, USA

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2 TITANIUM USED IN REFINERIES Presented by Stephen M. Patera LHI Metals

3 Titanium Grades Most Commonly Grade 2 Grade 7 Grade 12 Grade 16 Used in Refineries

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5 Corrosive Environments HCl Hydrochloric acid NH₄Cl Ammonium Chloride NH₄HS Ammonium Bisulfide

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7 ASME Design Allow./Unit Density (ksi/lb/cu in) Temperature ( F) Grades 2,7&16Ti Grade 3Ti Grade 12Ti 316L SS Alloy 625 C-276

8 Corrosion in Refineries R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

9 Corrosion in Refineries Controls operation of process line R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

10 Corrosion in Refineries Controls operation of process line Must be watched to prevent accidents. R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

11 Corrosion in Refineries Controls operation of process line Must be watched to prevent accidents. Causes reduction in heating and cooling efficiency R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

12 Corrosion in Refineries Controls operation of process line Must be watched to prevent accidents. Causes reduction in heating and cooling efficiency Requires periodic inspection and maintenance, which halts the entire production line. R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

13 Cost of Corrosion to Refineries R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

14 Cost of Corrosion to Refineries Corrosion costs $3.7 billion annually R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

15 Cost of Corrosion to Refineries Corrosion costs $3.7 billion annually $1.4 billion in equipment replacements. R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

16 Cost of Corrosion to Refineries Corrosion costs $3.7 billion annually $1.4 billion in equipment replacements. $1.8 billion in maintenance expenses. R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

17 Cost of Corrosion to Refineries Corrosion costs $3.7 billion annually $1.4 billion in equipment replacements. $1.8 billion in maintenance expenses. $0.5 billion in fouling removal. R. D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p

18 Crude Distillation Columns & Condensers

19 Corrosion Resistant Titanium Used in Refinery Service Chemistry O₂ Fe H₂ C N₂ Mo Ni Pd Ti Grade max 0.30 max max 0.08 max 0.03 max Balance Grade max 0.30 max max 0.08 max 0.03 max Balance Grade max 0.30 max max 0.08 max 0.03 max Balance Grade max 0.30 max max 0.08 max 0.03 max Balance

20 Titanium Mechanical & Physical Properties PROPERTY Grade 2 Grade 7 Grade 12 Grade 16 Tensile Strength (min) 50 ksi 50 ksi 70 ksi 50 ksi Yield Strength (min) 40 ksi 40 ksi 50 ksi 40 ksi Yield Strength (max) 65 ksi 65 ksi 65 ksi Elongation (min) 20% 20% 18 20%

21 Thank you and enjoy the show!

22 TITANIUM USE IN REFINERIES Stephen M. Patera LHI Metals S. Wixom Road Wixom, MI ABSTRACT This presentation will concentrate on the utilization of titanium products in refineries and why it is suited for this application. Titanium s use in refineries goes back decades, and has increased ever since. With the introduction of lower grade crudes and the corrosive nature of the subject environment, titanium is an ideal choice and lends itself to these applications. With data provided by a large oil company, we will examine several refining applications and the successful use of titanium in those applications. INTRODUCTION Titanium and its alloys offer excellent material options for use in refineries. With exceptional corrosion resistance in extreme environments, titanium has been used successfully for years in petroleum and petrochemical refining applications. Superior resistance to weak HCl, NH 4Cl, and NH 4HS has been the reason many refineries choose titanium for heat exchanger tubing and other applications. The challenge facing those in the titanium industry is the fact that carbon steel is still the preferred material for applications based on initial costs. Titanium producers and sellers need to demonstrate the long term advantages of utilizing titanium, by providing an analysis of the life cycle cost in these applications. A typical refinery will shut down portions of their plant for maintenance every 3 to 5 years. During these shutdowns heat exchangers will be inspected. Lower corrosion resistant materials such as carbon steel tubes will often require repair or replacement. Titanium heat exchanger tubes, with its superior corrosion resistance, will reduce maintenance costs improving the life cycle cost of the exchangers. Titanium will also reduce unexpected outages between scheduled shutdowns. Promoting titanium s reliable history in such applications, thus providing the customer with a maintenance free product that has a superior resistance to corrosion is a positive sales feature of the product. The greatest use of titanium in refineries is with water cooled heat exchanger bundles. The titanium is used to resist the aggressive conditions on the water side of the bundle. Titanium has progressed to be used in pressure vessels, shell & tube heat exchangers, air coolers, pipe, fittings and valves, where the harsh conditions on the process side are challenging. The vast majority of the titanium selected for these applications remains Grade 2; however, Grade s 7, 12 & 16 are now being used with more regularity. 1

23 Corrosion in Refineries Controls operation of process line. o Must be watched to prevent accidents. o Causes reduction in heating and cooling efficiency. o Requires periodic inspection and maintenance, which halts the entire production line. Cost of corrosion: $3.7 billion annually o $1.4 billion in equipment replacements. o $1.8 billion in maintenance expenses. o $0.5 billion in fouling removal R.D. Kane, Corrosion in Petroleum refining and Petrochemical Operations, Corrosion: Environments & Industries, Vol 13C, ASM Handbook, ASM International, 2006, p The major oil company providing data for this paper has successfully been using titanium exchangers in their crude distillation overhead service for greater than 25 years. Criteria for their use of titanium in their facilities are listed below as well as an examination of several of those applications: Grade 2 titanium has been used reliably up to 250 F (121 C) for over 25 years in atmosphere crude distillation column overheads when used in conjunction with injection of neutralizers to control the ph. Some failures have occurred when it was used above 250 F (121 C) in this service. Grade 2 titanium has also been used very successfully in fractionator overhead systems in other process units such as fluid catalytic crackers, delayed cokers, and sour water strippers. The temperatures of applications in these systems vary from 210 F (99 C) to 250 F (121 C). Grade 12 titanium has been used in atmospheric crude distilling column overhead condensers up to at least 340 F (171 C) in situations where formation of solid, dry salt can be avoided. Proper water wash or selection of amine neutralizers is important in ensuring the successful use of titanium. Deyuan Fan, William C. Fort, III, Richard J. Horvath, Equilon Enterprises, LLC; Experience with Titanium Heat Exchangers in Refinery Services 2

24 UTILIZATION OF TITANIUM IN PETROLEUM & PETROCHEMICAL REFINERIES CRUDE DISTILLATION COLUMNS & CONDENSERS Often time s lower grade crudes offer greater acidic hurdles. Crude overhead distillation units suffer corrosion, primarily from the presence of hydrogen chloride vapor. Calcium chloride and magnesium chloride salts in crude oil will hydrolyze at temperatures above 250 F, as the crude is heated in the distilling heater, (CDU), resulting in HCl. From the CDU, the HCl gas moves to the crude distilling column. It condenses with H₂O to become a hydrogen chloride solution, HCl, Hydrochloric Acid. Typically, refineries will partially neutralize the acid in the column with ammonia or amines to reduce and control corrosion. The resulting ammonium presents another corrosive situation, where titanium provides an ideal protective environment. Crude distillation column overhead service has been the home for the greatest number of early applications, and they have enjoyed great success in that environment. As compared to carbon steel, titanium has provided improved heat transfer, as well as protection from corrosion and pitting. Other refinery units, subsequent to the crude distilling units, such as fractionation towers (FCCU) and coking units (DCU) experience like harsh conditions. Titanium bundles in these applications have proven to provide far superior corrosion resistance than their carbon steel counterparts. Titanium offers superb resistance to concentrated ammonium bisulfide. Ammonium bisulfide is the result of sour water from crude tower overheads and from other sources that are stripped in sour water strippers, (SWS) to remove H₂S and ammonia. The resulting condensed water from the (SWS) column can contain as much as wt. % ammonium bisulfide. As mentioned previously, titanium offers resistance to corrosive environments, which also includes salt, brackish and polluted waters. As a large number of refineries are located in areas where this sort of water is used for cooling, titanium becomes an excellent choice. Titanium can easily handle polluted water, thus eliminating the need for water treatment, saving valuable time and financial resources. When the only available water is salt or brackish, titanium is a perfect choice, as it immune to attack in brine solutions within the limits specified in (Figure 1). In seawater, Grade 2 titanium has been used successfully at temperatures of 235 F 250 F, and generally performs very well. At temperatures above this, Grade s 12 & 16 are recommended to avoid possible chloride crevice corrosion under salt deposits or other potential crevices. Reference (Figure 1). Grade 16 has been recommended by the industry more often than Grade 12 over the past 10 years, as several refineries have experienced hydrogen embrittlement problems with Grade 12 due to the galvanic interactions with steel and H₂S. Grade 12 is 3

25 more susceptible to hydrogen absorption under these conditions and Grade 16 is equally competitive on the price side. That being said, Grade 12 has had its own success in refineries and can be offered under the right conditions. Figure 1 4

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27 CONCLUSION This review of titanium supports its application in refineries for a variety of reasons. During this time of limited petroleum resources, cost effective and efficient production is critical. Titanium s superior performance suggests the benefits substantially outweigh the costs. In comparison to the current use of carbon steel in these corrosive environments, titanium out performs in all aspects. REFERENCES 1. Dennis F. Hasson & C. Robert Crowe, Titanium for Offshore Oil Drilling, Journal of Metals, January William C. Fort, III & Deyuan Fan, Titanium Experience In Refining And Chemical Processes, 3. Gareth Hughes, Materials Of Crude Oil Refining: Corrosion Problems And Prevention, MSE 395 Final Presentation 4. Pieter Blauvelt, Dave Rowan, Brent Willey & Jim McMaster, Titanium Proven Performance In Hydrocarbon Processing,, Corrosion 2000, Paper # R.W. Schutz, RMI Titanium Company, Titanium: The Technically Correct Metal for Offshore Seawater Service,, 10th Anniversary Conference on Corrosion and Materials Offshore, September 14 15, 1994, Oslo, Norway 6. Deyuan Fan, William C. Fort, III & Richard J. Hovarth, Experience With Titanium Heat Exchangers In Refinery Services, Corrosion 2000, Paper # Timet, Titanium for Refinery Use, Technical Bulletin RT-2, March