Texaco GEMS G G 1 Material Selection Guide For Refinery Process Unit

DEC 97
MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS
GEMS G-G-1
TABLE OF CONTENTS PAGE 1. 2. INTRODUCTION ....................................................... COMMONLY USED ALLOYS ............................................... 2.1 2.2 2.3 3. Table of Nominal Composition ................................. ASTM Designations ............................................ Comparison of Materials ...................................... 3 3 3 3 3 10 10 16 17 20 21 21 22 23 24 26 27 27 27 31 32 34 39 39 39 40 40 40 41 41 41 42 43 43 43 44 45 45 45 50
REFINERY CORROSION AND OTHER FAILURES .............................. 3.1 3.2 3.3 3.4 Refinery Corrosion ........................................... Creep, Stress Rupture, and High Temperature Metallurgical Changes and Embrittlement .................................... Mechanical Damage, Overloading, Overpressuring, and Fatigue .. Incorrect or Defective Materials .............................
4.
MATERIAL SELECTION CRITERIA ........................................ 4.1 4.2 4.3 4.4 4.5 4.6 Predicted Corrosion Rate ..................................... Hydrogen Attack .............................................. Sulfidic Corrosion ........................................... Naphthenic Acid .............................................. Notch Toughness .............................................. Stress Corrosion Cracking .................................... 4.6.1 General............................................... 4.6.2 Hydrogen Embrittlement and Hydrogen Cracking. Wet H2S Cracking.............................................. 4.6.3 Caustic or Alkaline Cracking.......................... 4.6.4 Intergranular Corrosion and Cracking of Stainless Steels - Polythionic Acid Cracking.................... 4.6.5 Chloride Stress Corrosion Cracking.................... 4.6.6 Amine Cracking........................................ 4.6.7 Ammonia Cracking...................................... Scaling Resistance ........................................... Fuel Ash Corrosion ........................................... Elevated Temperature Strength ................................ High Temperature Microstructural or Chemical Changes and Embrittlement ................................................ 4.10.1 Hardening and Softening............................... 4.10.2 Grain Growth.......................................... 4.10.3 Graphitization........................................ 4.10.4 Temper Embrittlement and 885F Embrittlement.......... 4.10.5 Sigma Phase........................................... 4.10.6 Carburization and Decarburization..................... 4.10.7 Liquid Metal Embrittlement............................ References ...................................................
4.7 4.8 4.9 4.10
4.11 5.
MATERIALS FOR PROCESS UNITS ........................................ 5.1 5.2 5.3 General ...................................................... Crude Distilling Unit ........................................ Hydrotreater - Hydrocracker .................................. PAGE 1 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13
Catalytic Reforming Units .................................... Fluid Catalytic Cracking Units ............................... Alkylation Units ............................................. Gasification Units ........................................... Delayed Coking Units ......................................... Sour Water Treating .......................................... Sour Gas Treating Units ...................................... Sulfur Recovery Units ........................................ Tail Gas Treating Units ...................................... References ...................................................
55 56 60 61 66 68 69 71 71 71
TABLES 1 Nominal Chemical Composition of Commonly Used Alloys 2 ASTM Designations of Commonly Used Alloys FIGURES 1 Operating Limits for Steels in Hydrogen Service 2 Time for Incipient Attack of Carbon Steel in Hydrogen 3 High Temperature Sulfur Corrosion - Hydrogen Free Environment 3A Sulfur Corrosion Correction Factor 4 Predicted Corrosion Rates - Hydrogen-Hydrogen Sulfide Environment 5 Predicted Corrosion Rates - Hydrogen-Hydrogen Sulfide Environment 6 Predicted Corrosion Rates - Hydrogen-Hydrogen Sulfide Environment 7 Different Forms of Wet H2S Cracking 8 Conditions Requiring Streee Relief of Carbon Steel in Caustic Service 9 Stess Corrosion Cracking Austenitic Stainless Steels in Sodium Hydroxide (From Corrosion Resistance of Metals and Alloys. Second Edition, Edited by F.L. Laque and H.R. Copson, 1965) 10 Stress Corrosion Cracking of 18-8 Stainless Steel in Chloride Solutions (From R.A. White, E.F. Ehmke. Materials Selection for Refineries and Associated Facilities. NACE, 1991) 11 Relative 100,000 Hour Rupture Strength
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1.
INTRODUCTION 1. This guide is intended to give Engineering Department and refinery engineers background information on materials selection for refinery process units. Design of an individual unit may require some adjustment of materials. Materials selected in the process unit section are based on high sulfur crude. However, particular refineries should be able to process a variety of different crudes. Unexpected high general corrosion can cause extensive unit downtime and product loss. The information in this guide is general. More specific information can be found in industry references on hydrogen attack and sulfide corrosion. API RP 571 Recommended Practice for Recognition of Conditions Causing Deterioration or Failure and Corrosion in Petroleum Refining and Petrochemical Operations by J. Gutzeit, R. D. Merrick and L. R. Scharfstein published in ASM Metals Handbook, Ninth Edition, Volume 13, Corrosion, are good references. Readers are encouraged to make comments they feel are warranted based on their experience. Through information exchange and experience, a consensus in various problem areas can be gained.
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3.
2. 2.1
COMMONLY USED ALLOYS Nominal Composition See Table 1.
2.2
ASTM Designations See Table 2.
2.3
Comparison of Materials 2.3.1 Carbon Steel 1. 2. Reasons for Use: The most economical and readily available material. Problems a. b. c. d. e. f. 2.3.2 Low corrosion resistance. Low high temperature oxidation and sulfidation resistance. Low high temperature strength. Low notch toughness. Susceptible to stress corrosion cracking in aqueous sulfide, caustic, and amine solutions. Susceptible to hydrogen attack and graphitization.
Low Alloy (Carbon - 0.5 Mo) 1. Reasons for Use a. b. Higher elevated temperature strength than carbon steel. Years ago was believed to have increased resistance to hydrogen attack.
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2.
Problems a. b. c. Low notch toughness. Susceptible to graphitization and other problems associated with carbon steel. Since 1970, a series of hydrogen attack cases of 0.5Mo equipment has substantially reduced confidence in the position of the Nelson curve (see Section 4.2, Hydrogen Attack) for this steel. C - 0.5Mo steel is no longer recommended for new or replacement equipment in hydrogen service. Existing vessels operated in hydrogen service above carbon steel limits should be rigorously inspected periodically. Texaco no longer uses this steel for new equipment.
2.3.3
Low Alloy (1.25Cr-0.5Mo, 2.25Cr-1Mo, 5Cr-O.5Mo, 9Cr-1Mo) 1. Reasons for Use. a. Increasing Cr content yields increasing strength at elevated temperature, increasing oxidation, sulfidation (H2S or S), and hydrogen attack resistance. Molybdenum improves elevated temperature strength and creep resistance.
b. 2.
Problems a. b. Increasing Cr content results in higher cost. Welding becomes more difficult with pre- and post-heat treatment required.
2.3.4
AISI 4140, 4340 1. 2. Reasons for Use: Increased strength for compressor impellers and shafts. Problems: Special welding and heat treating required to minimize sulfide stress corrosion cracking.
2.3.5
2.5 Nickel, 3.5 Nickel 1. 2. Reason for Use: Increased low temperature notch toughness. Problems: Increased cost and welding problems over carbon steel.
2.3.6
Chromium Stainless Steel (Types 405, 410S, 410, 430, CA-15, CA-6NM) 1. Reasons for Use a. b. 2. Good resistance to non-acidic water solutions, sulfidation, oxidation, hydrogen attack. Low susceptibility to chloride stress corrosion cracking.
Problems a. b. c. Welding (especially with higher Cr content), poor elevated temperature strength. Tendency to pit in aqueous chlorides and sulfides. Embrittlement at 885F.
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d. e. f. 2.3.7
Sigma phase problems with greater than 12.5% Cr. Cost may be greater than austenitics. CA-6NM easier to cast and weld than CA-15.
E-Brite XM-27 1. Reasons for Use: Much higher resistance to stress corrosion cracking in chloride and caustic solutions than those of austenitic stainless steels. Problems a. b. Subject to embrittlement on extended exposure in 700F to 1060F temperature range. Strength falls off rapidly above 1000F.
2.
2.3.8
Cr-Ni Austenitic Stainless Steels (Types 304, 304L, 316, 316L, 317, 317L, 321, 347) 1. Reasons for Use a. b. c. d. Excellent corrosion resistance to many inorganic and organic acids and alkalis. Very good resistance to high temperature oxidation and sulfidation. 316 and 317 SS have good resistance to naphthenic acid corrosion. 321 and 347 SS are more resistant to sensitization and intergranular corrosion and cracking (such as polythionic acid cracking).
2.
Problems a. b. c. High cost. Very high susceptibility to stress corrosion cracking in wet chlorides. Very rapid intergranular corrosion and/or cracking (e.g., polythionic acid cracking) after sensitization by heating in temperature range of 700F to 1500F. L grades usually allow fabrication without sensitization but may sensitize after prolonged service in the above temperature range. For high temperature service, stabilized grades 321 and 347 are recommended. 321 may have poor strength at temperatures greater than 1100F. 347 has welding problems. 347 weld and weld overlay must be of the correct composition to prevent sigma phase formation and hot short cracking.
d.
e. f. g.
2.3.9
Cr-Ni Ferritic-Austenitic (Duplex) Stainless Steels (3RE60, 2205, 2507, CD-4MCu) 1. 2. Reasons for Use: More resistant to chloride stress corrosion cracking than austenitic (300 series) SS. Problems a. Higher cost versus austenitic SS and poor weldability.
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b. 2.3.10
Cannot be used for long periods at temperatures above approximately 570F.
Alloy AL-6XN and Alloy 20Cb3 1. Reasons for Use: Increased resistance to acids and chemicals and much less susceptible to chloride stress corrosion cracking than ordinary austenitics. Problems: Increased cost and more difficult to weld than ordinary austenitics.
2. 2.3.11
Incoloy 800 1. Reasons for Use a. b. 2. Good corrosion resistance (similar to ordinary austenitics). Better resistance to chloride stress corrosion cracking.
Problems: Usually costs more than ordinary austenitics and sensitizes.
2.3.12
Incoloy 825 1. Reasons for Use a. b. 2. Increased resistance to acids and chemicals. Much less susceptible to chloride stress corrosion cracking than ordinary austenitics.
Problems: Increased cost over austenitics.
2.3.13
Inconel 600 1. Reasons for Use a. b. c. d. 2. Good general corrosion and oxidation resistance. Good elevated temperature strength. Good resistance to chloride stress corrosion cracking. Excellent corrosion resistance in caustic.
Problems a. b. c. Poor sulfidation resistance above 1000F. Vulnerable to sensitization and intergranular cracking in some corrosives. Cost.
2.3.14
Inconel 625 1. Reasons for Use a. b. 2. Excellent high temperature strength and corrosion resistance. Very resistant to chloride stress corrosion cracking and sensitization.
Problems a. b. c. Cost. Availability Poor sulfidation, resistance above 1000F.
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2.3.15
Hastelloy B 1. Reasons for Use a. b. c. 2. Excellent corrosion resistance in reducing acids, such as HCl. Good high temperature strength. Very resistant to stress corrosion cracking.
Problems a. b. Cost. Availability.
2.3.16
Hastelloy C276 1. Reasons for Use a. b. c. d. e. Excellent corrosion resistance in oxidizing acids. Good high temperature strength. Very resistant to stress corrosion cracking. Resistant to sensitizing for much longer exposure time. Good corrosion resistance in reducing acids - second most corrosion resistant nickel alloy (after Hastelloy B) in hydrochloric acid.
2.
Problems a. b. Cost. Availability.
2.3.17
Monel 1. Reasons for Use a. Good general corrosion resistance to many chemicals, such as hydrochloric and hydrofluoric acids, aqueous sulfide, and caustic. Resistant to chloride stress corrosion cracking. Excellent resistance to seawater.
b. c. 2.
Problems a. b. c. Poor resistance to sulfidation over 400F. Embrittled by sulfur and heavy metals at low concentration during welding or heating. Corroded rapidly by aqueous ammonia or ammonium hydroxide at concentrations above approximately 3% weight.
2.3.18
Admiralty 1. Reasons for Use a. b. 2. Basic condenser tube material in cooling tower water. Adequate resistance in aqueous sulfides.
Problems a. Poor strength over 400F.
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b.
Dealloys (Zn) in water service. Addition of small amounts (0.03% to 0.05%) of arsenic (e.g., alloy C44300 per ASTM B111) substantially increases resistance to dezincification. Very susceptible to stress corrosion cracking in wet ammonia. Very rapid corrosion in ammonium hydroxide solutions. Very difficult to weld. Less resistant to seawater than aluminum brass and copper - nickel.
c. d. e. f. 2.3.19
Aluminum Brass 1. Reasons for Use: Similar to admiralty, except better in seawater, especially if fluid velocity is higher than 3 feet/sec. Problems: Similar to admiralty.
2. 2.3.20
Naval Brass 1. 2. Reasons for Use: Basic copper alloy tube sheet material compatible with admiralty and aluminum brass. Problems: Similar to admiralty and aluminum brass.
2.3.21
Copper Nickel 90/10 1. 2. Reasons for Use: Excellent in seawater. Problems a. b. Poor resistance to aqueous sulfides. Susceptibility to stress corrosion cracking in wet ammonia.
2.3.22
Copper Nickel 70/30 1. Reasons for Use a. b. c. d. e. 2. Excellent in seawater. Less susceptible to stress corrosion cracking in wet ammonia. Good strength. Good resistance to aqueous sulfides. Weldable.
Problems a. b. Higher cost than admiralty and aluminum brass. Will dealloy (Ni).
2.3.23
Aluminum Bronze 1. 2. Reasons for Use: Excellent resistance to seawater and weldable. Problems a. b. Cost. May require heat treatment.
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2.3.24
Aluminum and Its Alloys 1. Reasons for Use a. Excellent corrosion resistance in: (1) Atmospheric conditions (very resistant to rural, urban, and industrial atmospheres; lesser resistance to marine atmospheres). Fresh and cooling waters (except seawater). Hydrogen sulfide and carbon dioxide water solutions.
(2) (3) b.
Good resistance in concentrated (> 80%) nitric acid and organic acids (acetic, citric, tartaric, malic, fatty acids, etc.). High notch toughness at very low temperatures, not subjected to brittle fracture at cryogenic temperatures.
c.
2.
Problems a. b. c. d. e. Corrodes rapidly in acid (pH < 4.5) and alkaline (pH > 9.5) solutions. Poor resistance in solutions containing considerable amounts of chlorides, such as seawater. High sensitivity to galvanic corrosion (especially when in contact with copper and ferrous alloys). Very low strength at elevated temperature (over 400F). Most aluminum alloys have poorer corrosion resistance than pure aluminum. The latter has inadequate strength for many applications. Alclad 3003 alloy clad with Alloy 7072 (Al + 1% Zn) or with pure aluminum combines high corrosion resistance with improved mechanical properties. Aluminum tubes currently have limited application in refinery service because of fouling problems and pitting corrosion on the water side.
f.
2.3.25
Titanium and Its Alloys 1. Reasons for Use a. Combines comparatively high strength and very high strength-to-weight ratio with outstanding resistance in many extremely corrosive environments, including: (1) Seawater and other chloride salt solutions where stainless steels undergo pitting and stress corrosion cracking. Hypochlorites and wet chlorine. Nitric acid, including highly concentrated acids.
(2) (3) b. 2.
Titanium has very good low temperature strength.
Problems a. Increased cost.
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b.
Welding must be done in inert atmospheres or the metal becomes brittle due to absorbed gases (oxygen, nitrogen, and hydrogen). Titanium is not a good high temperature material, as it is embrittled in: (1) (2) Hydrogen above 480F. Air, oxygen, or nitrogen above 850F.
c.
2.3.26
Corrosion and Heat Resistant Cast Iron Ni-Resist 1. Reasons for Use a. b. 2. Good corrosion resistance in sour water, cooling water, and sea water. High resistance to high temperature scaling.
Problems a. b. Low notch toughness. Poor weldability.
3. 3.1
REFINERY CORROSION AND OTHER FAILURES Refinery Corrosion 3.1.1 General Corrosion is the destruction or deterioration of material caused by a chemical reaction with the materials environment. Metal corrosion is principally caused by thermodynamic instability of metals. In other words, the oxidized (corroded) state is more stable for the majority of metals than the reduced (metallic) state. Protecting refinery equipment from corrosion is extremely important. During operation, refinery equipment comes in contact with flammable hydrocarbon streams and toxic and/or explosive gases, often at high temperatures and pressures. Such contact aggravates the potential for corrosion problems, which: 1. 2. Substantially increases operating and maintenance costs. Drastically reduces equipment safety and can lead to serious accidents, such as fires and explosions. In many applications with high potential for corrosion and corrosion related failures of refinery equipment, safety considerations are the major concern, exceeding economic considerations in importance.
3.1.2
Causes of Corrosion Corrosion in refineries is not caused by processed hydrocarbons, which are mostly harmless with regards to corrosion. Corrosion problems result from various contaminants contained in the hydrocarbons, such as: 1. 2. 3. Water. Hydrogen sulfide and sulfur. Hydrogen chloride. PAGE 10 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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4. 5. 6. 7. 8. 9.
Carbon dioxide. Naphthenic acids. Polythionic acid. Inorganic and organic chlorides. Ammonia and ammonium bisulfide. Cyanides.
10. Phenols. 11. Others. Corrosive problems are also caused by process chemicals, such as: 1. 2. 3. 4. 5. 6. Sulfuric acid. Hydrofluoric acid. Phosphoric acid. Caustic. Amines. Various chlorides from catalysts.
In addition, corrosion problems are caused by: 1. 2. 3. 4. 5. 3.1.3 The atmosphere. Cooling water. Boiler feedwater. Steam condensate. Soil.
Common Types of Corrosion 1. General corrosion - thinning. Corrosion damage is spread more or less uniformly on the entire exposed metal surface. Local corrosion. Corrosion damage concentrates on local areas of the metal surface (e.g., pitting and crevice corrosion). Local corrosion usually has a far greater penetration rate than general corrosion. Local corrosion is much more difficult to detect in a timely manner through periodic inspections than uniform corrosion. For that reason, local corrosion is potentially more dangerous. Galvanic or two-metal corrosion occurs when two alloys with different electrode potentials are coupled in a water solution, soil, or other electroconductive environment. The more electronegative metal becomes the anode of the couple and undergoes accelerated corrosion. The more corrosion resistant metal corrodes very little or not at all (cathodic protection is based on this principle). Galvanic corrosion can be a major problem in seawater service, cooling water, and other water containing environments. It may also occur in the atmosphere. Stress corrosion cracking (SCC) is the fracture of alloys by a combination of corrosion and tensile stress. Failure frequently occurs in a rather mild chemical environment PAGE 11 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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under a tensile stress well below the yield strength of the material. In SCC, the stresses involved may be residual stresses in the metal, such as from bending or welding, or from uneven heating or cooling. Applied stresses, such as working stress from internal pressure or structural loading, also can be involved. In general, however, residual stresses are of prime importance in stress corrosion cracking. Only tensile stress results in SCC. Compressive stress, on the contrary, has a beneficial effect. Peening to introduce compressive stress has been used as a preventive measure under some circumstances. It has long been recognized that SCC is the most dangerous of the various types of corrosion failure of metals. SCC occurs unexpectedly and is extremely localized. As a rule, SCC is accompanied by little change in the equipment wall thickness. Therefore, it is very difficult to predict the occurrence of stress corrosion cracking and to take preventive measures in a timely manner. SCC can cause through fracture in very short periods of time (in the most severe cases in a day or even several hours). Various kinds of SCC are described in Section 4. 5. Intergranular corrosion is localized attack at and adjacent to grain boundaries. The alloy disintegrates (grains fall out) and/or loses its strength. Intergranular corrosion can be caused by noncorrosion resistant impurities at the grain boundaries or by depletion of the alloying elements (responsible for the alloy corrosion resistance) in the grain-boundary area. The latter mechanism accounts for intergranular corrosion of austenitic stainless steels (polythionic acid cracking) described further in Section 4. 6. Hydrogen damage is a general term which refers to mechanical damage of a metal caused by the presence of, or interaction with, hydrogen. It may occur at low temperature (e.g., hydrogen embrittlement in H2S water solutions) and at high temperature (hydrogen attack in high pressure hydrogen). Hydrogen damage is described further in Section 4. Selective leaching is the removal of one element from a solid alloy by corrosion processes. The most common examples of selective leaching in refinery application are dezincification of brasses and denickelfication in coppernickel alloys in cooling water systems. Corrosion under insulation occurs when insulation or fire proofing is allowed to become wet. Corrosion of underlying metal surfaces becomes a serious problem with piping and vessels operating below 250F because the metal is not hot enough to keep insulation dry during normal operation. The best preventive approach is to keep insulation dry in the first place. This means proper wrapping and caulking of joints. Metal surfaces near flanged connections should first be painted, since wetting of insulation, due to leakage, is likely to occur at such locations. In austenitic stainless equipment and piping, chloride containing insulation can cause stress corrosion cracking. PAGE 12 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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9.
Erosion corrosion occurs when protective surface films of corrosion products are damaged or worn away such that fresh metal is continuously exposed to corrosion. For this reason, alloys of aluminum, chromium steels, and stainless steels are especially subject to attack, since they depend on a surface film for the resistance to corrosion. Bends, elbows, and tees of piping, pump cases and impellers, compressor blades, valve internals, agitators, baffles, thermowells, and orifice plates are subject to various forms of erosion corrosion. In general, any increase in velocity will increase erosion corrosion, especially if suspended solids are involved. Flow turbulence at the inlet of heat exchanger tubes can result in rapid corrosion of the first 2 or 3 inches of the tubing. Erosion corrosion due to droplets of liquid suspended in a vapor stream is a real problem in many refinery applications. Known as impingement corrosion, this type of erosion corrosion occurs in overhead piping and condensers of distillation towers, when vapor velocities exceed 25 ft/sec. The usual cause is water droplets that contain dissolved hydrogen sulfide and hydrochloric acid. Areas most likely to be attacked are elbows in overhead piping, condenser shell inlet nozzles, and condenser upper tube rows.
3.1.4
Mechanisms of High Temperature and Low Temperature Refinery Corrosion For practical purposes, refinery corrosion can be divided into two categories: high temperature corrosion and low temperature electrolytic corrosion. The latter requires the presence of liquid water. High temperature corrosion starts at approximately 450F and occurs through the mechanism called chemical corrosion. It represents the interaction of metal with the corrosive environment, when oxidation of the metal and reduction of the oxidizing component - oxidizer (oxid.) of the environment occur in one step: Me+Oxid. MeOxid. (e.g., 4Fe+302 2Fe203 or Fe+H2S + FeS+H2) (e.g., oxidation of steel in hot air, corrosion in high temperature hydrogen sulfide.) Corrosion mechanism in electrolytes, such as water solutions (low temperature refinery corrosion), is more complicated and is called electrochemical corrosion. The main feature of electrochemical corrosion is that ionization of metal (anodic reaction) and reduction of the oxidizer (cathodic reaction) occur in more than one step. In this case, overall corrosion reaction consists of at least two separate half cell reactions: Anodic Reaction, Ionization of Metal Cathodic Reaction, Reduction of Oxidizer
Me Men+ + ne
Oxid. + ne Oxid.ne (e.g., 2H+ + 2e H2 - hydrogen reduction
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or O2 + 2H2O + 4e 4OH- - oxygen reduction.) Overall Corrosion Reaction Me + Oxid. Men+ + Oxid.ne (e.g., Fe + H2SO4 FeSO4 + H2 or 2Fe + 2H2O + O2 2Fe+2 + 4OH- 2Fe(OH)2
As shown in the above reaction equations, the electrochemical mechanism includes the flow of released electrons from the anodic area to the cathodic area on the metal surface. The anodic and cathodic reactions are separated from each other and occur either at the same time on different areas of the corroding surface (heterogeneous electrochemical mechanism) or at a different time on the same surface (homogeneous electrochemical mechanism). In the latter case, the entire corroding surface alternatively works at one moment as an anodic area and at another as a cathodic area. In refinery corrosion, the heterogeneous electrochemical mechanism with space division of anodic and cathodic reactions prevails. Examples of electrochemical corrosion are corrosion in diluted acids, alkalis, seawater, other natural waters, cooling water, soil, atmosphere, H2S, and/or CO2 water solutions. It should be noted that in the temperature range between the high temperature corrosion starting point and water condensation point (above which no electrochemical corrosion is possible) corrosion practically does not occur. 3.1.5 Environmental Effects The most important environmental factors influencing corrosion rate are content of oxygen and other oxidizers, pH, corrosive concentration, temperature, and velocity. Except for passivated alloys (such as stainless steels, aluminum, and titanium), where formation of the surface oxide film drastically reduces the corrosion rate, increase of oxygen or other oxidizer content usually increases the rate of corrosion. As a rule, decrease of pH (increase of acidity) substantially increases rate of corrosion. Concentration increases in the corrosive environment generally increase corrosion rates. However, corrosion in concentrated acids often is minimal because of small water content or formation of a protective film on corrosion products. Temperature increases corrosion rates, as with almost all chemical reactions. Another temperature effect should be considered in refinery operations. Increased temperatures increase the amount of water in liquid hydrocarbon and vapor streams. This means that more water condenses in downstream distillation towers or in overhead condensing systems. As a result, corrosion occurs in equipment thought to be dry.
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Corrosion by strong acids, such as concentrated sulfuric acid in alkylation units, is highly dependent on temperature. Carbon steel can be used for these units primarily because temperatures are relatively low. Stainless steels can exhibit a drastic change in corrosion resistance as temperature reaches a certain level. This manifests itself as a sudden loss of passivity, causing the corrosion rate to increase by a factor of 100 or more. Metal skin temperature rather than process stream temperature should be used to predict the corrosion rate. Increase of flow velocity will cause removal of the protective corrosion product film and thereby raise the corrosion rate. 3.1.6 Corrosion Protection Detailed descriptions of all corrosion preventive methods are beyond the scope of this guide. The most commonly used methods will be discussed briefly. Proper metal selection is the most common method of corrosion prevention. Some of the natural alloy-corrosive combinations are: 1. 2. 3. 4. 5. 6. 7. 8. 9. Stainless steels - nitric acid. Nickel and nickel alloys - caustic. Monel - hydrofluoric acid. Hastelloys (Chlorimets)-hot hydrochloric acid. Lead - dilute sulfuric acid. Aluminum - noncontaminated atmospheric exposure. Tin - distilled water. Titanium - hot strong oxidizing solutions and highly concentrated chloride solutions. Tantalum - ultimate corrosion resistance.
10. Carbon steel - concentrated sulfuric acid. The above list does not represent the only material - corrosive combinations. There are two main mechanisms of metal corrosion resistance: 1. 2. Thermodynamic stability when metal is chemically inert in some media (e.g., gold, platinum, copper). Formation of a protective corrosion product film which effectively retards further corrosion (stainless steels, aluminum, titanium, etc.).
Relatively thin coatings of metallic, inorganic, and organic materials can provide an effective corrosion protective barrier between the metal and its environment. Metal coatings are applied by electroplating, flame spraying (metallizing), hot dipping, cladding, weld overlaying, vapor deposition, etc. Inorganic coatings are applied by spraying, diffusion, or chemical conversion. Porosity or other defects in coatings can
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result in accelerated localized attack on the base metal because of galvanic corrosion effect, etc. Changing the environment to reduce corrosion includes lowering temperature, changing velocity, removing oxygen or oxidizers, and changing concentration. Inhibitors (substances which, when added in small concentrations to an environment, substantially decrease the corrosion rate) and neutralizers (e.g., caustic and soda ash) are frequently added for corrosion control. Certain design rules should be followed for best corrosion resistance. 1. Gaps, crevices, and other stagnant, difficult to access zones should be avoided. Corrosive agents can accumulate and concentrate in such areas. If possible, small closed voids should have provision of drain holes. Tanks and other containers should be designed for easy draining and cleaning (sloped bottoms toward drain holes, etc.) Systems should be designed to enable the easy replacement of components that are expected to corrode rapidly in service. Excessive mechanical stresses and stress concentrations in components exposed to corrosive mediums should be avoided. Electrical contact between dissimilar metals should be avoided to prevent galvanic corrosion. Sharp bends and other areas of rapid direction change in piping systems should be avoided since they can promote erosion corrosion. Dissimilar metals, uneven heat and stress distributions, and other differences between points in the system should be avoided since they may lead to corrosion damage. Conditions should be as uniform as possible throughout entire system. Cathodic protection and anodic protection are based on the use of direct electric current either from a rectifier (impressed current system) or by contact with a more electronegative anodic metal (sacrificial anode system). 3.2 Creep, Stress Rupture, and High Temperature Metallurgical Changes and Embrittlement 3.2.1 Creep and Stress Rupture Creep and stress rupture strength are important mechanical properties for alloys used at high temperatures. Many steels and alloys that have good high temperature corrosion resistance possess insufficient mechanical properties for long-term use at elevated temperatures. Aluminum and its alloys are an example. Creep is the continuous plastic deformation of a metal under applied stresses below normal yield strength that occurs at high temperature.
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4. 5. 6.
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Stress rupture is the failure resulting from creep for an extended period of time. Creep is the combined effect of temperature, stress, and time that causes the formation of voids and fissures at grain boundaries and results in bulging or cracking. In some cases, it is an intergranular, brittle type of fracture with very little, if any, deformation prior to rupture. Hence, normal visual inspection might not reveal an impending failure. Creep in carbon steel becomes a problem above 650F. For instance, long-term stress of 11,500 psi causes stress rupture of carbon steel at 900F. This can be compared to a short-term tensile strength of approximately 54,000 psi for the same steel at the same temperature. Stress rupture failures in refineries are usually associated with fired heater tubes and fired boilers. Most of these failures are a result of overheating and local hot spots in the furnace caused by faulty burners, inadequate control of furnace temperature, and coke or scale deposits within the tubes. Bulging or hot spots are signs of impending failure. 3.2.2 High Temperature Metallurgical Changes and Embrittlement In addition to creep and stress rupture, metals and alloys exposed to high temperature undergo microstructural and chemical changes that may cause substantial metal degradation. The most significant of such metallurgical changes are graphitization, temper embrittlement, 885F embrittlement, and sigma phase formation. All these changes, as well as chemical changes, such as carburization and decarburization, are described in more detail in Section 4. 3.3 Mechanical Damage, Overloading, Overpressuring, and Fatigue 3.3.1 Mechanical Damage Mechanical damage to refinery equipment is a common cause of failure. Typical examples are the misuse of tools and other equipment, wind damage, and carelessness of handling when equipment was moved or erected. Other types of loading on structural columns that are normally designed for compressive loading may lead to bending. Supports may have been damaged when used as anchors for winches. During earth moving work, underground pipelines and electrical conduits may have been damaged if they were not carefully located and properly identified. Flange faces and other machined seating surfaces may have been damaged when not protected with covers or when not handled with care. Material improperly thrown from truck beds may have been bent, crushed, or cracked. Tubes of heat exchanger tube bundles may have been crushed if the bundles were not lifted with proper slings. Equipment and structures are normally designed to withstand any anticipated wind loading. During construction or repairs, however, wind damage may have occurred if components were not properly reinforced. Loose sheets of metal, boards, and the
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like may have been blown about by high winds if they were not properly secured. Wear or mechanical abrasion (erosion) is a significant problem in refineries and accounts for many failures. Catalyst movement in FCC units and coke handling in coking units are examples of wear associated with refinery processes. Wear in pumps, compressors, and other rotating machinery is common in the refining industry. Many parts designed for abrasion service are made of some grade of austenitic manganese steel because of that alloys outstanding toughness coupled with good wear resistance. Hardenable carbon and medium alloy steels and abrasion resistant cast irons are also used. A large assortment of alloys is available for abrasive service, including wrought alloys, sintered metal compacts, castings, and hard surfacing materials. They can be roughly classified, in descending order of abrasion resistance and ascending order of toughness, as follows: 1. 2. 3. 4. 5. 6. 7. Tungsten carbide coating and sintered carbide compacts. High chromium cast irons and hardfacing alloys. Martensitic cast irons and hardfacing alloys. Austenitic cast irons and hardfacing alloys. Pearlitic steels. Ferritic steels. Austenitic steels, especially 13% manganese type.
Hardness is often thought to be a property that is indicative of good wear resistance. It must, however, be considered with discretion when evaluating an alloy's suitability in abrasive situations. Hardness should only be considered after its relation to a given service has been proven. Simple and widely used hardness tests, such as Brinell or Rockwell, tell almost nothing about the hardness of microscopic constituents which are very important to good wear resistance. Cavitation damage is caused by the rapid formation and collapse of vapor bubbles in liquid at a metal surface as a result of pressure variations. Calculations have shown that bubble collapse can produce shock waves with impact pressures sufficiently high to produce plastic deformation in most metals. In brittle metals, cracking and metal loss occurs as grains are torn out of the surface. Corrosive conditions accelerate cavitation damage. In refineries, cavitation occurs mostly on the backside of pump impellers. Certain areas of piping components, such as elbows, can also become subject to cavitation damage. Vibration can also lead to cavitation. Damage is usually in the form of closely spaced pitting. Cavitation cold work hardens the surface layer of most metals. This can be detected by metallurgical examination of the damaged part. Cavitation damage can be reduced by techniques similar to those listed for erosion corrosion.
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3.3.2
Overloading 1. Overloading occurs when loads in excess of the maximum permitted by design are applied to equipment. Hydrostatic testing of vessels can overload supporting structures due to the excess weight applied. Excessive bending stresses may be induced in vessel shells when pipe support brackets are attached. Addition of piping to existing pipe supports or piping that is left overhanging on supports may present overloading problems. Overloads can also occur where metal members have been weakened as a result of corrosion, wear, fire, or change in shape or position. Thermal expansion and contraction cause many overloading problems, unless flexible connections are properly provided. Piping subject to thermal expansion may force a centrifugal pump or steam turbine out of line and warp the shaft, unless the pipe is anchored near the equipment.
2.
3.3.3
Overpressuring Overpressuring may be defined as the application of pressure in excess of the maximum allowable working pressure of the equipment under consideration. With low excess pressure, there is little chance of damage occurring. When excess pressures are high, failures causing loss of life and property can occur. Overpressuring causes buckling, bulging, ruptures, and splits.
3.3.4
Failure Overloading and overstressing usually result in ductile failure, which is accompanied by an appreciable amount of deformation before failure and, therefore, takes a lot of energy. Brittle failure is rapid, often catastrophic, takes very little energy, and results in a fracture surface with a grainy appearance. Brittle fracture occurs in metals: 1. 2. Under rapid loading at temperatures below the ductile to brittle transition temperature. That have been embrittled by service in some environments (hydrogen, wet H2S, carburization, etc.) or some dangerous temperature range (graphitization, temper embrittlement, sigma phase formation, etc.).
Brittle fracture results from a loss of ductility, whereupon the steel is referred to as having low notch toughness or poor impact strength. The loss of impact strength can result in brittle fracture, not only upon actual impact loading but under conditions of more or less constant stress. Brittle fractures, unlike ductile failures, occur without warning. Lack of warning and the rapid and extensive propagation of cracks account for the fact that such failures are often catastrophic. Some brittle failures of tanks and pressure vessels have occurred during hydrostatic or pneumatic testing. For this reason, it is generally the policy to refrain from testing while ambient temperatures are low, particularly if the testing medium is also cold. In any case, the test PAGE 19 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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pressure should be applied as slowly as practical in order to avoid sudden increases in stress. 3.3.5 Fatigue Fatigue is the failure of a component by cracking after the continued application of cyclic stress. Below a definite stress limit, cyclic stressing of a metal does not affect the material and no cracking occurs, regardless of the passage of time. This stress limit is called the endurance limit or fatigue limit. At stresses higher than the endurance limit, a crack initiates and is propagated by continued application of stress cycles. Eventually the component fails, usually from a single crack. Little deformation of the metal occurs, and the failure appears to be brittle. Generally, the endurance limit of steels is roughly 50% of the tensile strength. The endurance limit for non-ferrous alloys ranges from 30% to 50%. Brittle steels are more likely to fail by fatigue than ductile steels. A large number of failures in refineries have been attributed to fatigue or corrosion fatigue. The latter occurs when local corrosion (such as pitting) promotes the mechanical fatigue. Prime examples are reciprocating parts in pumps and compressors, shafts of rotating machinery, boiler feedwater deaerator drums, etc. Only tensile stress produces fatigue crack growth. Compressive stress will not cause fatigue. Fatigue failure can be prevented by proper design, which includes eliminating stress raisers, using radii instead of sharp corners, and avoiding stamping and other sharp-edged marks, as well as cold straightening bent parts that will later be subjected to in-service cyclic stress. Other remedies are hardening the surface layer (e.g., nitriding, carborizing) or eliminating tensile stress in the surface layer (e.g., shot peening). Post weld heat treatment is also helpful. 3.4 Incorrect or Defective Materials Many failures in refineries are caused by incorrect or defective materials. Incorrect materials principally result from mix-ups by suppliers. For example, during construction of one refining unit, approximately 30% of piping and fittings failed to meet specifications in one way or another. Often, suppliers may substitute what they consider to be an equivalent or better material than that specified. Suppliers do not realize that a stainless steel fitting is not necessarily an improvement over a carbon steel fitting, especially with regards to pitting corrosion or stress corrosion cracking. The substitution of castings for wrought or forged shapes often leads to problems. Casting defects, such as shrinkage, sand holes, or blowholes not visible from the exterior of the casting, can create unforeseen cracking and corrosion problems. Shrinkage cracks are often found in the
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thinner sections where the cast metal cools faster. Sharp corners and abrupt changes in cross sectional area are stress raisers. Shrinkage cracks can occur at such points. Discontinuities in wrought material are excellent crack initiators. The discontinuities may be laminations and crevices which can cause hydrogen blistering in certain applications. To expedite repairs during a shutdown, material substitutions may be necessary. Often, the correct material simply cannot be obtained because of the long time required and unreasonably high minimum quantity purchase requirements. Intentional upgrading can also lead to problems (as in the above case of stainless steel fitting replacement). To avoid costly problems arising from the use of incorrect materials, development of a metallurgical verification or positive material identification (PMI) program is recommended for each project. PMI should be performed on alloy materials of the following types: 1. 2. 3. 4. 5. 6. 7. 8. 9. Plates and forgings and other pressure vessel components. Piping. Flanges. Fittings. Welds. Valve parts. Bolts and nuts. Exchanger and heater tubes. Elements of pumps and compressors.
The extent of testing may vary for different projects and may be from 5% - 10% to 100%. Methods of testing include: 1. 2. 3. 4. Portable optical emission spectrometer. Portable X-ray fluorescence analyzer. Chemical spot tests per ASTM STP 550, Nondestructive Rapid Identification of Metals and Alloys by Spot Test. Laboratory analysis on coupons or drillings, using a laboratory grade optical emission spectrometer, laboratory grade X-ray fluorescence analyzer, or wet chemical analysis.
4. 4.1
MATERIAL SELECTION CRITERIA Predicted Corrosion Rate The predicted rate of corrosion during the service of designed equipment and piping is an extremely significant factor that governs material selection. Each type of equipment has a certain design life that is considered the minimum time that it must be in service before replacement. Texaco standards on equipment design life are:
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DESIGN LIFE OF EQUIPMENT Equipment Type Piping, Small (less than 18 inch NPS) Piping, Large (18 inch NPS and larger) Furnace Tubes Vessel Shells (including nozzles) Internals (non-removable) Internals (removable) Trays Exchanger Shells (including nozzles) Exchanger Tubes: Carbon Steel Alloy Material Air Cooled Exchangers (including headers, tubes) Pump Casings
Life, Years 10 20 10 20 20 10 10 20 5 10 10 20
The exact corrosion rate expected cannot be easily determined for many applications. Approximate, reasonably conservative values are therefore used. Based on the approximate predicted corrosion rate, the corrosion allowance (CA) that is needed to provide a designed equipment item with the desired design life can be selected. For example, a designed pressure vessel with an expected corrosion rate of 12 mils per year or 12 mpy (1 mil = 0.001 inch) should have a minimum CA of 12 mpy x 20 years, which equals 240 mils or 0.24 inch. Typical CAs are: 1. 2. 3. Carbon steel pressure vessels - 1/8 inch and 1/4 inch. Carbon steel and low alloy piping - 1/16 inch, 1/8 inch, and 3/16 inch. Stainless steel piping - as low as 1/32 inch.
If the above CAs do not provide the required design life, more corrosion resistant material or other anticorrosive methods (such as cladding, coatings, inhibitors) should be used. The above rule may have some exceptions. 4.2 Hydrogen Attack Gaseous hydrogen does not appreciably permeate steel at atmospheric temperature. However, at elevated temperatures and pressures, molecular hydrogen dissociates into atomic form, which then permeates the steel. Within the steel, hydrogen reacts with iron carbide or dissolved carbon to form methane, which causes decarburization and cracking. The chemical reaction is as follows: C(Fe) + 2H2 CH4 Where: C(Fe) indicates carbides or dissolved carbon. The methane formed cannot diffuse out of the steel. Accumulation of methane in internal voids results in the development of high stresses that ultimately fissure, crack, or blister the metal. This accumulation, which affects the load carrying ability of the equipment, is called PAGE 22 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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hydrogen attack. The addition of chromium and molybdenum to steel increases carbide stability and resistance to hydrogen attack. Early data on hydrogen attack was plotted by George Nelson of Shell Development. The Nelson Curves have been widely accepted as design criteria. Nelson's work was assumed by the American Petroleum Institute and is discussed in API Publication 941, Steels for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants. Laboratory and operational data are plotted to show safe operating conditions of temperature and hydrogen partial pressure for carbon and various low alloy steels (Figure 1). A second curve (Figure 2) shows the effect of time on hydrogen attack for carbon steel. It should be noted that, in this edition, the curve for C - 0.5Mo steel has been removed from the Nelson Curves Graph (Figure 1). Since 1970, a series of unfavorable service experiences has reduced confidence in this steel. The current edition of API 941 cautions users about a potential danger of using C - 0.5Mo steel above the Nelson Curve for carbon steel and recommends rigorous periodic inspection (UT examination) for such applications. Texaco no longer uses this steel and instead utilizes 1.25Cr-0.5Mo with the additional requirement of a minimum chromium content of 1.25%. Texaco's normal design practice is to stay 50F below the curve for a particular steel. In vertical sections of the curve, Texaco normally uses an equivalent safe hydrogen partial pressure. It should also be indicated that hydrogen attack has been found in both the gas phase and the all-liquid hydrocarbon phase that is in equilibrium with the gas hydrogen phase. The hydrogen attack curves form the basis for material selection for hydrogen processing units. Materials may need to be upgraded, clad, or overlaid for corrosion protection. The upgraded material or backing steel must be resistant to hydrogen attack at the process design conditions. (Maximum operating temperature shall be 50F below the steel Nelson curve.) In no case shall the mechanical design temperature be above the Nelson curve. 4.3 Sulfidic Corrosion Corrosion by various sulfur compounds at temperatures above 500F is a common problem in many petroleum refining processes. The corrosion mechanism is believed to include conversion of sulfur compounds to hydrogen sulfide, followed by reaction of H2S with steel. Corrosivity of sulfur compounds generally increases with temperature. Corrosion control depends on the formation of a metal sulfide film that becomes much more protective in the presence of chromium. Thus, the addition of chromium increases steel resistance to high temperature sulfidic corrosion. For the purpose of materials selection, high temperature sulfidic corrosion is broken into two parts, depending on whether or not hydrogen is present. Sulfidic corrosion without hydrogen occurs primarily in various components of crude distillation units, catalytic cracking units, and
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hydrotreating and hydrocracking units upstream of the hydrogen injection. Prediction of sulfidic corrosion rate in a hydrogen free environment can be made based on the modified McConomy curves (Figure 3), which summarize multiyear refinery experience. The corrosion rates found on the curves should be multiplied by a correction factor shown on Figure 3A for process streams with various sulfur contents. As the figures show, doubling the sulfur content can increase the corrosion rate by approximately 30%. Plant experience has shown that the sulfidic corrosion rate in the absence of hydrogen starts to decrease as temperatures exceed 850F. The decrease can be attributed to the formation of a protective coke layer and decomposition of reactive sulfur compounds (such as H2S). Sulfidic corrosion in the presence of hydrogen is typical for hydrotreating and hydrocracking operations. Hydrogen increases the severity of high temperature sulfidic corrosion, presumably by converting organic sulfur compounds in feed stocks to hydrogen sulfide. Modified Couper-Gorman corrosion rate curves, which are being used for elevated temperature sulfide corrosion in hydrogen containing processes, are shown on Figures 4, 5, and 6. The estimated corrosion rate, services involved, and desired design life determine the material and its corrosion allowance. Rates of up to 10 mils per year are usually considered acceptable. However, consideration must be given to potential downstream pressure drop problems that result from scale buildup. Many times, corrosion rates can be tolerated from the mechanical standpoint, but equipment fouling and/or pressure drop problems for units with long anticipated runs must be considered. While these curves form a reasonable basis to select materials, other data, such as sulfur distribution and evolution curves for a particular crude, may be very helpful. 4.4 Naphthenic Acid Naphthenic acids occur naturally in some crude oils. During distillation, these acids tend to concentrate in higher boiling point fractions such as heavy atmospheric gas oil, atmospheric resid, and vacuum gas oils. The acids may also be present in vacuum resid, but often many of the more corrosive ones will have distilled into the vacuum sidestreams. Lower boiling point streams are usually low in naphthenic acids. Typical problem areas are in crude distillation units, heater outlets, transfer lines, atmospheric and vacuum towers, and side stream strippers. Naphthenic acid problems may be aggravated by leakage of oxygen into the vacuum systems. Appearance of Naphthenic Acid Corrosion: Naphthenic acid corrosion and H2S sulfidic corrosion occur at roughly the same temperature ranges. However, they can be easily distinguished from each other by the appearance of the corrosion. Naphthenic acid corrosion generally has cavities and craters with sharp edges or channels and grooves with little or no corrosion product on the surface. Such corrosion is generally the severest or localized to turbulent areas. The surface of the metal is scale free because the naphthenic acid corrosion product, PAGE 24 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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iron naphthenate, is soluble in hot hydrocarbons. In contrast, when H2S corrosion is dominant, a thick, adherent, protective iron sulfide film is present, and the metal surface is smoothly and uniformly corroded. In most cases, either naphthenic or H2S corrosion is observed with no evidence of the other mechanism being present as if one mechanism is dominant to the exclusion of the other. However, under threshold conditions, in some cases, corrosion in turbulent areas is observed that is smooth in appearance without an adherent, protective FeS film. Corrosion rates in such cases are far greater than would be predicted for H2S corrosion alone. Naphthenic acid can be considered a primary contributor to such corrosion. Temperature: Naphthenic acid corrosion typically has been observed in the 450F to 750F temperature range. Above 750F, the naphthenic acids either break down or distill into the vapor phase. Naphthenic acid corrosion occurs only where liquid phase is present. The corrosion increases with temperature up to the acids decomposition and/or complete vaporization temperature. Sulfur Content in the Crude: At low temperatures, certain sulfur compounds may reduce the severity of naphthenic acid corrosion. At such temperatures, the sulfide film may offer some degree of protection from the naphthenic acid corrosion provided the velocities are not high. At higher temperatures, the presence of naphthenic acids increases the severity of sulfidic corrosion. It appears that the presence of the naphthenic acids disrupts the sulfide film thereby promoting sulfidic corrosion on alloys that would normally resist this attack. Naphthenic Acid Content is a very important factor in naphthenic acid corrosion and is generally expressed in total acid number (TAN) or neutralization number that is the amount of KOH in milligrams required to neutralize 1 gram of stock. Until recently naphthenic acid corrosion would have been considered a possibility at neutralization numbers greater than 0.5 for the whole crude or any gas oil range cuts. Most serious naphthenic acid problems were believed to occur with neutralization numbers greater than 1.0. But both ASTM methods being used for naphthenic acid content determination, ASTM D974 and ASTM D664, do not differentiate between naphthenic acids, phenols, carbon dioxide, hydrogen sulfide, mercaptans, and other acidic compounds present in the oil. In addition, the two methods, when compared, do not yield the same results. ASTM D664 yields TAN numbers that are 30% to 80% higher than ASTM D974. However, these ASTM methods are the only tests that produce values that are sufficiently documented at present to permit comparison of crude corrosivity. Thus, prediction of crude corrosivity based on the TAN alone could be highly misleading. For assessment of plant corrosion effects, the naphthenic acid content needs to be determined for each cut in order to predict exactly where the acids will concentrate during the distillation of crude. The isolation and analysis of naphthenic acids from crude oil may be performed adequately with methods, such as UOP 565 and UOP 587, by chromatographic separations, or other available analytical techniques. Nalco has a technique that will provide the NAT (naphthenic acid titration) number from a crude or side cut sample. The NAT number is now appearing more frequently in the literature as the true measure of acidity to better characterize the naphthenic acid corrosivity.
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Velocity: The flow regime has a significant effect on naphthenic acid corrosion. The higher the acid content, generally, the greater the sensitivity to velocity. In some cases, it appears possible to obtain very high corrosion rates even at relatively low levels of naphthenic acid content (i.e., TAN 0.3) and low sulfur content when combined with high temperature and high velocity. Fluid velocity has long been used as the parameter for comparing flow in pipes, heater tubes, and heater trays and also for comparing laboratory data to the field. However, fluid velocity has been found to lack predictive capabilities and is being replaced by parameters related to fluid flow, such as the field shear stress and the Reynolds number. Field shear stress, rather than velocity, is the parameter directly proportional to corrosion through removal of the normally protective films. The field shear stress is proportional to all of the following: 1. 2. 3. Density and viscosity of fluid and vapor in pipe at a specified temperature. Degree of vaporization in the pipe. Pipe diameter.
Materials: The materials most vulnerable to naphthenic acid corrosion are carbon steel (corrosion rate may be as high as 1,000 mils per year) and the iron-chrome (5%-12% Cr) alloys commonly used in corrosive refining services. 12% Cr may experience corrosion rates greater than those of carbon steel. The molybdenum containing austenitic stainless steel (Type 316 or Type 317 SS) are required for resistance to greater acid concentrations. It has been found that a minimum Mo content of 2.5% is required in Type 316 SS to provide the best resistance to naphthenic acids. Naphthenic acid corrosion can be controlled by blending crude oils that have high neutralization number with other crude oils. Blending is designed to reduce the naphthenic acid content of the worst sidecut. When blending is insufficient to prevent attack, affected areas can be alloyed with Type 316 or 317 SS. 4.5 Notch Toughness Selection of materials for pressure containing parts must adequately consider notch toughness requirements. Notch toughness is a measure of the ability of a material to absorb rapid or impact loading without fracturing. Significant factors are the type of steel used, the operating and ambient temperatures, and the required thickness. Certain carbon steels and low alloys have considerably better notch toughness at room temperature than others. The lower the temperature and the thicker the equipment, the more emphasis must be placed on notch toughness. Notch toughness is typically measured by Charpy V-notch test bars. The bar is broken by impact at a specified temperature, and the energy required to fracture the bar is recorded. Although considerations can become very complex, energy absorption greater than 15 ft-lb to 20 ft-lb at a specified temperature is usually considered adequate to minimize notch toughness problems that could lead to brittle failure. Some critical pressure equipment items, such as high temperature, high pressure hydrogen reactors may have a more stringent energy absorption requirement (e.g., 40 ft-lb). Because of an increasing awareness of brittle failure, notch toughness criteria are becoming more significant in the selection of steels for pressure containing parts. In designing equipment to operate at low temperatures (especially in the subzero range below 32F or 0C), problems associated with notch PAGE 26 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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toughness becomes extremely important. The majority of steels and alloys show a tendency toward a sharp decrease of notch toughness and an increase in the possibility of undergoing brittle fracture at these lower temperatures. The list of steels used at very low, subzero, and cryogenic temperatures includes (in the order of increasingly low temperature notch toughness): 2.5% nickel 3.5% nickel 5% nickel 9% nickel A A A A 203 GRA&B, A 334 GR7, A 333 GR7 203 GRD&E, A 334 GR3, A 333 GR3 645 353, A 333 GR8, A 334 GR8
and austenitic stainless steels. Iron - nickel alloy Invar M63 (36% Ni), as well as some aluminum and titanium alloys, also possess high values of low temperature notch toughness. 4.6 Stress Corrosion Cracking 4.6.1 General Most materials used in refinery service can fail due to stress corrosion cracking. Failures may occur without prior warning, and potential problems are often difficult or impossible to predict. Stress corrosion cracking results from a combination of stress and corrosive environment. Many materials have high cracking susceptibilities in certain environments. Since refinery processes often contain the necessary corrosive environment, considerable emphasis must be placed on selection of materials and on how the material is fabricated and used. Several types of stress corrosion cracking are briefly described. It is important for designers to recognize that many of the problems can be minimized by controlling the environment and fabrication of equipment. 4.6.2 Hydrogen Embrittlement, Hydrogen Cracking, and Wet H2S Cracking Hydrogen embrittlement affects many materials. In refinery service, it normally causes problems with carbon steel, low alloys, and chromium stainless steels. Cracking results from high stresses and hydrogen pickup due to acid or wet hydrogen sulfide corrosion and is often promoted by cyanides in the FCCU gas recovery streams. The most widespread is wet H2S cracking. Hydrogen sulfide is a relatively mild acting corrosive to carbon steel. General corrosion rates tend to be not very high. However, during the mild corrosion process, considerable amounts of hydrogen can be liberated. The hydrogen can have several significant, detrimental effects on the refinery equipment metal. Atomic hydrogen (H) and molecular hydrogen (H2) are produced in the corrosion reaction of steel with aqueous H2S as follows: Fe + H2S FeS + 2H followed by 2H H2 Under ordinary conditions, molecular hydrogen produced by the above corrosion reaction harmlessly evolves away. If hydrogen sulfide is present, it acts as a negative catalyst and discourages the reaction 2H H2. This permits the atomic hydrogen to accumulate on the metal surface and penetrate steel PAGE 27 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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where its presence in the crystal structure affects mechanical properties. Other poisons that promote the entrance of atomic hydrogen into steel are cyanide, phosphorous, antimony, selenium, and arsenic ions. Atomic hydrogen is much smaller than molecular hydrogen. As a result, only atomic hydrogen can diffuse through the steel's microstructure. Upon reaching lattice flaws, nonmetallic inclusions, and other void type defects, the atomic hydrogen can form molecular hydrogen, causing a pressure build up that is sufficient to produce local ruptures and fissuring. Aside from corrosion, sources capable of charging a steel with hydrogen are acid pickling and cleaning operations, plating, welding, and cathodic protection. Hydrogen charging in wet H2S may cause hydrogen embrittlement or cracking. The latter involves four types of mechanisms: sulfide stress cracking, hydrogen blistering, hydrogen induced cracking, and stress oriented hydrogen induced cracking (Figure 7). Hydrogen embrittlement occurs during the advanced stage of hydrogen saturation of steel. The structure becomes brittle as a result of the many strains imposed on the lattice structure by the presence of hydrogen. In such cases, the structure will fracture instead of deforming when subjected to stress. Harmless micro-cracks introduced by fabrication, heat treatment, or welding exist in most structures. In the absence of hydrogen, they are harmless. In the presence of hydrogen, sudden brittle failure at low stress levels can result. In general, harder, higher strength steels are more susceptible to hydrogen embrittlement than lower strength steels. Sulfide stress cracking (SSC) is cracking attributed to hydrogen in high strength, low ductility microstructures that can be identified by high hardness. It is highly dependent on a steel's composition, microstructure, strength, residual stress, and applied stress levels. Small, localized hard zones in welds and weld heat affected zones can initiate SSC, even if bulk material hardness is quite low. Sulfide stress cracking is also seen in hardened components, such as valve trim and compressor springs, that are exposed to wet sulfide environments. Resistance to SSC can be provided by tempering or postweld heat treatments, which reduce hardness to 200 Brinell Hardness Number (BHN) or lower. Postweld heat treatment reduces residual stresses and tempers the microstructure, thereby providing SSC resistance. If cracking of standard 12% chromium steel valve trim is a problem, a change to austenitic stainless steel can be considered. High strength bolting can be given a modified temper to reduce hardness and, thereby, the tendency to crack. Hydrogen blistering occurs when hydrogen atoms that diffuse into the steel enter any available internal defects (such as inclusions or voids). These hydrogen atoms will combine there to form hydrogen gas (H2) that cannot diffuse out of the steel. Blistering occurs because of the buildup of local hydrogen gas pressure in these internal defects. Elongated MnS stringers found in older pressure vessel steels and banding of pearlite and ferrite phases both act as sites for absorbed hydrogen accumulation and thus the initiation of blisters. Very often, PAGE 28 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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blisters become apparent on the metal surface. Increasing blister growth can produce tears to the surface and result in a loss of pressure containing capability. Hydrogen induced cracking (HIC) also results from hydrogen gas build up, but it produces only internal (subsurface) cracks and small blisters without showing up at the surface. In many cases, cracking is described as stepwise cracking. Like blistering, HIC is not stress dependent. Stress oriented HIC (SOHIC) can be considered a special case of HIC, in which a stack of small fissures that are formed in the steel are oriented perpendicular to the applied stress. The small fissures can become linked and form a leak path through the thickness of the steel which makes this failure more dangerous. SOHIC is often found adjacent to a weld where the residual stresses are high, because SOHIC is stress dependent. Hydrogen embrittlement and cracking affects pressure vessels, piping, and tanks, as well as pumps, compressors, valve springs, impellers, and hardware. Remedial actions include reduction or elimination of hydrogen activity. This can be done by using alloy or alloy clad materials or nonmetallic coatings resistant to hydrogen producing corrosion or by inhibiting the corrosion process. For stress dependent failures, such as sulfide stress cracking or SOHIC, post weld heat treatment and hardness limitation (not to exceed 200 Brinell) are very beneficial. Texaco guidelines mandate PWHT for pressure vessels, heat exchangers, air coolers, pumps, and compressors in wet H2S service. Service is considered wet H2S if it contains free liquid water and H2S concentration equal to, or exceeding, any of the following values: a. Partial pressure in vapor phase of 0.25 psi. b. Content in water phase of 50 wppm. c. Content in liquid hydrocarbon phase of 250 wppm. Hardness after PWHT shall not exceed 200 Brinell. Hydrogen blistering, HIC, and SOHIC may be controlled by limiting the sulfur content in steel (to decrease the amount of MnS inclusions where gas hydrogen tends to accumulate) and shape control of these inclusions. Based on this approach, so called HIC resistant steels were developed. The term HIC resistant is used by manufacturers and users to denote conventional grades of steel (e.g., ASTM A 516-70) that have been metallurgically processed to enhance their resistance to HIC. Such processing typically includes ultra-low sulfur levels (i.e., < 0.002 weight % sulfur), normalizing heat treatments to modify the hot rolled microstructure, and possibly Ca additions to produce sulfide shape control. Shape control is important in that it produces sulfides of spherical morphology that reduce localized stresses in the vicinity of the inclusion, compared to the elongated stringers found in conventional steels. These steels are often tested to evaluate HIC resistance using conventional or modified NACE TM0284 methods for the purposes PAGE 29 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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of lot acceptance or for supplemental information. These steels typically have improved resistance to HIC as compared to conventional steels. However, the latest CLI International research showed that the currently used HIC resistant steels in some cases are more susceptible to SOHIC than conventional steels(Cayard, et al, see references). CLI International currently recommends using low sulfur conventional steels in the applications that require the use of HIC resistant steel. The sulfur content should be 0.005% to 0.010%. S lower than 0.005% may promote SOHIC. For the purpose of wet H2S cracking protection, the affected refinery equipment is divided into 3 categories. Category 1 Service H2S concentration is 50 to 2,000 ppmw in water phase, which corresponds to partial pressure of H2S gas of 0.25 psi to 10 psi. No known cyanide compounds or cyanide concentration less than 20 ppmw. No previous experience of significant blistering, HIC, or SOHIC. Protective measures. Pressure vessels: Killed carbon steel, PWHT, hardness not to exceed 200 Brinell. Piping: Killed carbon steel, hardness not to exceed 200 Brinell. Category 2 Service H2S concentration is above 2,000 ppmw in water phase or 10 psi in gas phase. Presence of hydrogen cyanide or other cyanide compounds (more than 20 ppmw in water phase). Previous experience shows significant blistering, HIC, or SOHIC problems. Protective measures. Pressure Vessels: Killed carbon steel normalized or quenched and tempered. Sulfur content in steel 0.005% to 0.010%, maximum phosphorus content of 0.010%. Each plate should be 100% UT in accordance with ASME SA-578S1.1 with level III acceptance standards. PWHT, hardness not to exceed 200 Brinell.
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Piping: Killed carbon steel, hardness not to exceed 200 Brinell. Category 3 Service Acidic aqueous phase with pH value below 4.5. High concentrations of acid gases H2S and CO2. History of high rate corrosion and significant cracking and/or blistering. Equipment in critical service when failure can cause explosions and fire. Protective measures. Pressure Vessels: Corrosion resistant liners, such as 304L SS or 316L SS cladding and weld overlay, organic coatings, etc. Piping: Corrosion resistant materials, such as 304L or 316L SS. In some cases, sulfide stress cracking of carbon steel pressure vessels resulted from the use of certain welding wire-flux combinations during fabrication. Some of the welding procedures resulted in abnormally high weld hardness and caused unexpected sulfide cracking failures. As a result, certain welding restrictions have been placed on fabricators of carbon steel equipment. Very specific heat treating restrictions have been placed on compressor manufacturers to limit the yield strength of impellers and other highly stressed parts to 90,000 psi. The added requirement of utilizing a heat treatment, such that no untempered martensite is formed, greatly minimizes potential sulfide stress cracking problems. 4.6.3 Caustic or Alkaline Cracking Caustic stress corrosion cracking is a result of high stresses in caustic or other alkaline environments. Cracks are intergranular. Most materials used in refinery applications can have cracking problems. Cracking usually takes place in caustic service and boiler applications. Alkaline cracking occurs if conditions lead to partial dissolution or breaks in normally protective corrosion product film on the metal surface. Cracking is not related to weld hardness. Temperature-related caustic cracking occurs for carbon steel above a temperature range of 120F to 180F (Figure 8) and for stainless steels above a temperature range of 220F to 400F (Figure 9), depending on caustic concentration. The potential of overheating from steam or electrical tracing of caustic equipment or piping to keep the caustic in solution should be taken into account when considering temperature factor. The common remedial action is to stress relieve the fabricated equipment to reduce residual stresses.
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Figure 8 shows which conditions require PWHT of carbon steel to prevent caustic cracking. 4.6.4 Intergranular Corrosion and Cracking of Stainless Steels Polythionic Acid Cracking 1. Sensitization If austenitic SS is heated or cooled through the temperature range of 700F to 1500F, the chromium along grain boundaries tends to combine with carbon to form chromium carbides. This process is called carbide precipitation or sensitization. Carbon diffuses towards the grain boundaries quite rapidly in the sensitizing temperature range, but chromium is much less mobile. As a result, all carbon in the alloy and only the chromium located in the areas adjacent to the grain boundaries are available for chromium carbide formation. The net effect is a depletion of chromium (which is the basic reason for corrosion resistance of SS) and a drastic fall of corrosion resistance near grain boundaries. Sensitization is a time dependent process. There is a complex relationship between temperature and time to sensitization. 2. Sources of Sensitization Sensitization may result from slow cooling during heat treatment and other fabricating processes (hot rolling, bending, etc.) or welding. Welding is probably the main source of austenitic SS sensitization. The problem in this case is aggravated by large size and complexity of welded equipment and piping, which makes implementation of the protective measures very difficult. Normal welding procedures utilizing arc welding can induce sensitization. Generally, the higher the heat input during welding, the higher the probability of sensitization. Sensitization from welding usually occurs in zones of the base metal slightly away from the weld (heat affected zones) rather than at the weld itself. Sensitization can also result from operation in the sensitizing temperature range of 700F to 1500F. 3. Failure of Sensitized Stainless Steel The depletion of the chromium content at grain boundaries of sensitized SS substantially decreases corrosion resistance of the grain boundaries. The metal becomes susceptible to rapid intergranular (along grain boundaries) failure. The intergranular attack rate is accelerated by galvanic effect due to electrode potential difference between grains and boundary areas. Grain boundaries are anodic versus grain, and the area ratio is very unfavorable (large cathode - grain, small anode - grain boundary). Damage rate on exposure of a sensitized SS to a corrosive environment depends on severity of the environment and extent of sensitization. In sea water, a sensitized SS sheet may fail within weeks or months. In a boiling solution containing CuSO45H2O (13 gm/l) and H2SO4 (47 ml concentrated acid/l), which is used as an accelerated test PAGE 32 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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medium, failure occurs within hours. The intergranular corrosion may also occur in comparatively mild media (dilute weak acids, both organic and inorganic, etc.). Intergranular damage of sensitized SS can manifest in intergranular corrosion or (in presence of applied stresses or residual stresses in the metal) in intergranular cracking. In refinery applications, the most widespread intergranular cracking of SS is polythionic acid cracking. Polythionic acids of the type H2SxO6 (where x varies from 3 to 6) are formed by the reaction of oxygen and water with the sulfide film that is present on SS surfaces as a result of high temperature sulfidic corrosion. This cracking occurs during shutdown periods when oxygen and water are available from steam or wash water used to remove hydrocarbons before inspection or simply from atmospheric exposure. 4. Measures to Prevent Intergranular Corrosion Three main methods are used to control or minimize intergranular corrosion of austenitic SS. a. Heat Treatment at 1920F to 2000F Followed by Quenching (Solution Anneal) The high temperature treatment dissolves precipitated carbides in the austenitic matrix solid solution, and rapid cooling prevents their reformation. This treatment is recommended, for example, after welding operations. It is not always a feasible treatment, however, because of structure size and/or a tendency to warp during cooling. b. Reduction of Carbon Content This reduction does not allow sufficient carbide to form to cause intergranular attack. Alloys of low carbon content, e.g., < 0.03% C, are designated by the letter L, e.g., Types 304 L SS, 316 L SS. These alloys can be welded or otherwise heated in the sensitizing temperature range with much less resultant susceptibility to intergranular corrosion. However, they are not immune and may sensitize after prolonged exposure in the sensitizing temperature range (700F to 1500F). c. Addition of Elements that Form Stable Carbides These elements (Ti or Cb) have much greater affinity for carbon than chromium and are added in sufficient amounts to combine with all of the free carbon in the steel. Thus, carbides of the stabilizing elements form rather than chromium carbides. Alloys of this kind are called stabilized grades, e.g., Types 321, 347, 348 SS. They can be welded or otherwise heated within the sensitizing range without becoming susceptible to intergranular corrosion. In welding operations, the weld rod usually contains Cb rather than Ti. Titanium tends to oxidize (burn out) at elevated temperature, with the danger of its residual concentration becoming too low to stabilize the weld alloy against intergranular corrosion. Columbium, on
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the other hand, is lost by oxidation to a lesser extent. Unfortunately, even stabilized grades under certain conditions can undergo intergranular attack in a very narrow zone immediately adjacent to the weld (called knife-line attack). This knife-line attack is caused by dissolving all stabilizing elements carbides. The dissolution results from high temperature and rapid cooling during welding. After this, the stabilizing element carbides are no longer helpful. For best resistance, heat treatment at 1600F to 1650F after welding (stabilizing anneal) is required to reprecipitate stabilizing element carbides. Texaco guidelines for SS require use of low carbon grades for all welded items and stabilized grades for services at temperatures of 700F and higher. Another method of protecting austenitic SS equipment from intergranular cracking involves neutralizing the polythionic acids or other acid solutions (that may form during shutdown periods) with soda ash wash. Suitable procedures to prevent cracking are outlined in NACE document RP0170. These procedures include nitrogen purging of components that were opened to the atmosphere, purging with dry air that has a dew point below -15C (5F), or neutralizing any acids that are formed by washing components with a 2% aqueous soda ash (sodium carbonate) solution. Soda ash solution can also be used for hydrotesting austenitic SS equipment prior to returning components to service. Residues of soda ash solution should be left on components during temperature storage to prevent SCC. High nickel alloys (especially those not containing stabilizing elements Cb and Ti, such as Incoloy 800 and Inconel 600) are also susceptible to intergranular corrosion and cracking. Chemically stabilized alloys, such as Incoloy 825 and Inconel 625, are much more resistant to sensitization. To enhance corrosion resistance of Incoloy 825, Inco Alloy International recommends the following: 1. Final hot working should be done in a temperature range of 1600F - 1800F. 2. Additional stabilizing annealing at 1725F - 1800F is suggested if the material is to be welded or subjected to further thermal treatment. Rapid cooling (forced air or water quench) may be desired for heavier sections. 4.6.5 Chloride Stress Corrosion Cracking Austenitic stainless steels are susceptible to stress corrosion cracking in waters and wet environments containing chlorides. Chloride SCC usually appears as transgranular, highly branched cracks. In several cases, sensitized microstructures have undergone intergranular cracking in chlorides.
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The main factors contributing to chloride SCC include chloride concentration, temperature, pH, oxygen content, stress level, and susceptibility of steel. 1. Chloride Concentration As a general rule, it may be accepted that the more concentrated the chloride, the more likely SCC becomes. The concentration of chloride ions capable of causing SCC depends upon the condition of the other factors listed above. At 10 ppm, the time to cracking in laboratory tests increases so much that this concentration may be considered safe at most conditions which can be encountered in oil refinery applications. Stress corrosion cracking of austenitic stainless steels 18-8 (such as 304L SS) at various chloride concentrations is shown in Figure 10. It should be emphasized that chloride concentration in water can increase because of partial water vaporization. Such vaporization can make a formerly safe solution unsafe. Therefore, it is recommended that any design of SS equipment which includes concentrating mechanisms, such as wetting and drying cycles and crevices, be avoided. 2. Temperature Temperature is an important factor in chloride SCC. It seldom occurs, except at elevated temperatures above approximately 130F. Metal temperature, rather than process-side, water-in or water-out temperatures, is important regarding chloride SCC. SS pump impellers in sea water service have shown no cracking problems despite the presence of chloride and high oxygen content. Cracking has occurred, however, at tropical locations, where exposure to direct sunlight could increase metal temperature above ambient. 3. pH Acid chloride solutions are more often encountered when SCC occurs. However, slightly alkaline solutions, too, can cause SCC, although it may require longer time and higher temperatures than in acid solutions. In alkaline solutions, the likelihood of chloride SCC is greatly reduced. 4. Oxygen Content Oxygen appears to be necessary for chloride SCC in neutral solutions, where oxygen reduction is the primary cathodic reaction in the corrosion portion of stress corrosion cracking. In acid chloride solutions, where hydrogen reduction is the primary cathodic reaction, SCC can occur even when the oxygen concentration is quite low. The oxygen concentration in boiling magnesium chloride solution at 311F (which causes quick SCC of austenitic SS) has been determined to be just 0.3 ppm. Actually, oxygen is not necessary for cracking in acidic solutions, such as MgCl2. On the other side, in neutral solutions, as oxygen content increases, fewer chlorides are necessary for SCC to occur.
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This explains why, in some practical applications, stainless steel components, such as heat exchanger tube bundles, do not crack until removed from operation and exposed to air during shutdown. 5. Stress Increasing the stress decreases the time before cracking occurs. The minimum stress required to cause chloride SCC depends on temperature, alloy composition, and environment composition. In some cases, it has been observed to be as low as approximately 10% of the yield stress. In other cases, cracking does not occur below the yield stresses. From a practical standpoint, it can generally be assumed that residual fabricating stresses, especially at welds, alone or in conjunction with normal operating stresses, are sufficient to cause chloride SCC in as-fabricated alloys that are susceptible to chloride SCC. Even stress relieving heat treatments do not completely prevent chloride SCC. 6. Susceptibility of Alloys The greatest susceptibility to chloride SCC is exhibited by SS with a nickel content of 8% (which is the nominal composition for 304 SS). Greater resistance is shown by alloys of either lower or higher nickel contents. Four non-quantitative categories of relative susceptibility may be identified among austenitic SS: a. b. c. d. Highest susceptibility - sulfur bearing 303 and 301 and sensitized 304. Intermediate susceptibility - nonsensitized 304, 304L. Lower susceptibility - 316, 316L, 309. Lowest susceptibility - 310, 314, 18Cr-18Ni-2Si (XM-15).
Alloys are classified as either resistant or immune to chloride SCC, depending on how they perform in accelerated laboratory tests. In general, an alloy is immune if it passes the boiling 42% magnesium chloride test conducted in accordance with ASTM G 36. Examples are Inconel 600, E-Brite (26Cr-1Mo), and commercially pure titanium. The industry has recognized the severity of this test. Some alloys that fail the G 36 test but pass less severe laboratory tests (e.g., boiling 25% sodium chloride), such as Incoloy 800 and 825, austenitic-ferritic (duplex) SS 2205 and 2507, and Carpenter 20Mo-6 (20Cr-35Ni-6Mo), typically provide many years of service in water-cooled heat exchangers. Unfortunately, all of the immune and resistant alloys are more expensive than traditional 300 series SS. It is generally recognized that alloys with greater than approximately 40% nickel are immune to chloride SCC. 7. Mechanism Modern corrosion theory considers the mechanism of chloride SCC to be of an electrochemical-mechanical nature. The corrosion resistance of stainless steels is not based on their thermodynamic stability. It is caused by the
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formation of surface thin passive oxide film, which protects the metal from further corrosion. Chlorides, being highly corrosive, cause partial damage of this passive film, which results in the formation of small pits on the metal surface. These pits act as a stress raiser. The highly stressed pit bottom becomes anodic in relation to the rest of the surface that is covered with the film. These pits dissolve at a high rate and form a crack. The crack growth by metal dissolution continues until the crack reaches the critical size. It then starts to propagate by fracture mechanics mechanism. Eventually mechanical failure occurs. The above mechanism of a strongly localized process explains why chloride SCC occurs without any appreciable general corrosion. 8. Main Sources of Chlorides in Refineries a. b. c. d. e. f. g. Chloride salts from crude oil, produced water, and ballast water. Water condensed from process stream (process water). Cooling water, wash-up water, and fire water. Boiler feedwater and stripping system. Catalyst. Residue from hydrotest water and other manufacturing operations. Hydrogen that is used in hydrotreating and hydrocracking processes may form hydrogen chloride, for example, by reacting with chlorides in oil, catalyst, reactor refractory lining, amine solution carryover, etc. Ammonia, which also may be present in the process stream, can react with hydrogen chloride and form ammonium chloride. The latter at temperatures lower than 400F to 450F forms deposits and leaves a source of chlorides on the metal surface. Both hydrogen chloride and ammonium chloride, when dissolved in condensed water, will form acid chloride solutions (NH4Cl is an acid salt due to hydrolysis) which are very aggressive from an SCC standpoint. Insulation may also be the chloride source and cause the retention of water and chloride concentrating under insulation. Chloride SCC may occur during service or down periods, depending on the time chloride containing solutions are present in the process equipment. It may start not only on the inside surface but also on the outside metal surface (for example, by wash-up water, fire water, atmospheric precipitations, or under insulation). In one case, chloride SCC was caused by seawater spray carried by prevailing winds. The spray soaked the insulation over 304 SS line, chlorides were concentrated by evaporation, and cracking occurred in the areas with residual weld stresses. Other cases of cracking under insulation have resulted from water dripping on insulated pipe and leaching chlorides from insulation. PAGE 37 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
h.
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9.
Measures to Prevent Chloride SCC a. Use of resistant alloys. Ferritic SS, such as 405 (12Cr), 430 (17Cr), and E-Brite (26Cr-1Mo), are not susceptible to chloride SCC and can be used instead of austenitic SS, if allowed by their corrosion resistance and mechanical properties. Duplex SS (2205 and 2507) also have high resistance to cracking. Higher alloy materials (Inconel, Incoloy, Carpenter 20Cb-3, etc.) can be used. In practice, SS and nickel alloys containing greater than 30% Ni are immune to chloride SCC in most refinery environments. b. Use of austenitic SS as an internal cladding rather than as a base metal. Cracking would be arrested on the interface between the cladding and base metal. If possible, use of carbon steel with a heavy corrosion allowance instead of SS. In SS equipment and piping design, avoidance of gaps and crevices where water solution can be trapped, concentrate in chloride, and cause cracking (e.g., use of butt full penetration welds instead of socket weld). If possible, holes should be used to drain small closed voids. Minimization of the amount of water and oxygen that enters the system under all circumstances (washing, shut down, operations, etc.). If some water coming into the system is unavoidable, the chloride content should not exceed 10 ppm. The oxygen content in the water should be kept to a minimum by blanketing with non-oxygen gas, such as nitrogen with the addition of ammonia. Each time after water enters the system, it should be drained thoroughly during start up by flushing with dry kerosene or equal. An alternative to low chloride water is an aqueous 0.5% sodium nitrate solution, recommended by NACE Standard RP-01-70 as a chloride cracking inhibitor for SS. Caution: excess NaNO3 can cause SCC of carbon steel. Ammonia should be added to nitrogen, steam, or any other gas used during start-up and shutdown. Ammonia should be added in the concentration to ensure that any condensate has a pH of 9 or above. f. The following measures are recommended to prevent chloride SCC under insulation: (1) Using insulation that conforms to ASTM C 795, Specification for Thermal Insulation for Use in Contact with Austenitic Stainless Steel. Protective coating of the vessel or piping before insulation (epoxy, silicon-base coating, etc.). Installation of aluminum foil under insulation. This method is claimed to provide both a physical barrier to chloride migration to SS surface, as well as sacrificial cathodic protection to SS if the insulation becomes wet.
c. d.
e.
(2)
(3)
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(4)
Installation of electric or steam heat tracing systems to maintain the external SS surface temperature at a higher level than the water dew point to prevent water condensation under insulation.
4.6.6
Amine Cracking Carbon steel is susceptible to SCC in rich and lean amine solutions. Cracking in fresh, uncontaminated amine solutions has not been observed so far. Amine cracking appears to be similar in many ways to alkaline cracking. Cracks are intergranular and form in places where protective film of corrosion products break. Cracking is not related to weld hardness. The common remedial action is to stress relieve all of the fabricated equipment and piping regardless of service temperature.
4.6.7
Ammonia Cracking Ammonia cracking in refineries is typically seen in copper alloy heat exchange tubing. Admiralty and aluminum brass are very susceptible to cracking when stressed and exposed to aqueous environments containing ammonia or ammonium compounds especially in the presence of air. The common remedial action is to specify 70-30 Cu-Ni, which is more resistant to cracking. Water wash is recommended for brass condenser tubes before exposure to air to wash out deposits containing ammonium compounds. Monel corrodes rapidly in high pH ammonia environments. In some isolated cases, it has cracked when highly stressed in sour water with ammonia present. Carbon and alloy steels are subject to cracking in contact with anhydrous liquid ammonia at room temperature. Cracking is avoided by stress relieved heat treatment and/or by addition of 0.2% water, which acts as an inhibitor.
4.7
Scaling Resistance The following table shows the maximum temperatures in atmospheres of air, steam, or flue gas at which the various alloys withstand excessive scaling. These temperatures should be considered approximate and may change significantly, depending on the specific atmosphere. MATERIAL Carbon Steel 2.25Cr-1Mo 5Cr-0.5Mo 9Cr-1Mo SS Type 410 SS Type 304, 316, 321, 347 SS Type 310 (25Cr-20Ni) MAX. TEMP. w/o EXCESSIVE SCALING (F) 1000 1100 1150 1200 1300 1600 1900
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4.8
Fuel Ash Corrosion Fuel ash corrosion is a potential problem in heaters and boilers if burning high sulfur (approximately 2% plus) fuel oil with 50 ppm or more vanadium. The sulfates and vanadates formed during combustion combine and become liquid compounds in the 1150F to 1300F range. The liquid is very corrosive and will attack heater and boiler parts that are normally scaling resistant. Current solutions to the fuel ash problem include: 1. 2. Limiting maximum tube wall temperature to 1200F based on practical experiences. Adding magnesium and aluminum oxides to the fuel oil. These materials raise the melting point of the sulfate - vanadate compounds so they do not liquefy. Using special alloys, such as 50Cr-50Ni. The 50Cr-50Ni alloy may give several times the service life than that expected for standard heater and boiler alloys. Certain refractory coatings have been reasonably successful.
3.
4. 4.9
Elevated Temperature Strength For comparison purposes, the 100,000 hour stress to rupture versus temperature curves for several commonly used alloys are shown in Figure 11. Elevated temperature strength as stress to rupture and percent creep in 100,000 hours determine the allowable stress for recognized codes, such as ASME, if operating in the creep range (above 800F). API 530, Recommended Practice for Calculation of Heater Tube Thickness in Petroleum Refineries, specifies the following limits for design metal temperatures for different alloys. MATERIAL Carbon Steel Carbon Steel - 0.5Mo 1.25Cr-0.5Mo 2.25Cr-1Mo 3Cr-1Mo 5Cr-0.5Mo 5Cr-0.5Mo-1.5Si 7Cr-0.5Mo 9Cr-1Mo SS 304, 304H, 316, 316H, 321, 321H, 347, 347H Incoloy 800H HK-40 (Cast Fe-25Cr-21Ni-0.5Mo, ASTM A 608 GR HK 40) MAXIMUM DESIGN METAL TEMP. (F) 1000 1100 1100 1200 1200 1200 1300 1300 1300 1500 1800 1850
4.10
High Temperature Microstructural or Chemical Changes and Embrittlement Elevated temperature exposure causes metallurgical changes to occur in many of the metals and alloys used in refinery service. Many of the microstructural changes are time and temperature dependent. Some are reversible. The possibility of microstructural changes that may result in embrittlement, decreased strength, or notch toughness must be considered when selecting materials. PAGE 40 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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4.10.1
Hardening and Softening Hardening of steels is the result of martensite formation after heating to above the lower critical temperature (1340F for carbon steel) followed by rapid cooling. A brittle martensitic carbide structure is formed that is not desirable for refinery equipment and piping. Hardening can occur in the course of welding fabrication or if steels are exposed to severe overheating, such as in a fire. Hot bending can also be a source of hardening. Welding of carbon steels with less than 0.25% carbon generally presents no hardening problems, because the usual cooling rates are not fast enough to permit martensitic formation. However, carbon steel with more than 0.35% carbon, low alloy steels, and martensitic straight chromium stainless steels will harden simply by air cooling after welding. Similarly, during fire exposure, these hardenable materials can become extremely hard and brittle to the extent that they are not serviceable. To prevent cracking of hardened metal after welding, preheat treatment and postweld heat treatments are used. In the case of fire damaged material, hardness surveys using portable testers can be used to identify equipment and piping hardened by overheating and quenching. Conversely, softening can also be a problem with refinery equipment. Some pressure vessels are made of low alloy steels that are quench and tempered or normalized and tempered to optimize design strength. Subsequent welding, heating for bending, or exposure to fire can degrade strength properties such that replacement or reheat treatment will be required. Commonly used bolting, ASTM A 193 Grade B7, is an example of an intentionally hardened component. Hydroprocessing thickwall reactors made of 2.25Cr-1Mo material are another example.
4.10.2
Grain Growth Grain growth occurs if steels are heated above a certain temperature, beginning at approximately 1100F for carbon steel. It is most pronounced at 1350F. The amount of growth depends on the maximum temperature reached and the length of time at temperature. Austenitic stainless steels and high nickel-chromium alloys do not become subject to grain growth until heated to above 1650F. Grain growth lowers the room temperature tensile strength and notch toughness but increases both creep strength and rupture strength. In practice, grain growth has not been a significant factor in refinery failures. It is, however, very useful for pinpointing furnace operational problems that have led to localized overheating failures of furnace tubes. Metallographic examination of the microstructure of failed components can reveal, through grain growth, the temperature to which the component was exposed. This technique is also applied to refinery fire damage evaluations.
4.10.3
Graphitization Graphitization problems can occur with carbon and carbon 0.5Mo steels operating above approximately 850F. PAGE 41 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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Graphitization represents decomposition of the iron carbide phase into iron and graphite. If the graphite particles form a continuous line through the thickness of a pressure part, the load carrying ability of the part may be seriously decreased. The stress rupture strength is also drastically reduced. Weld heat affected zones usually tend to have more graphitization problems. Some carbon steels are more susceptible to graphitization than others. Carbon - 0.5Mo can be very susceptible. Steels with chromium added form stable enough carbides that resist the graphitization. 4.10.4 Temper Embrittlement and 885F Embrittlement Temper embrittlement is a microstructural change that occurs with time between approximately 700F and 1000F. Room temperature notch toughness drops very significantly. It happens most often in low alloy chrome-moly steels. The embrittlement is easily identified by its effect on the brittle-to-ductile failure transition temperature in impact tests, such as the Charpy V-notch test. In extreme cases, a steel that starts out with a transition temperature of -120F can, after long exposure to temperatures in the embrittling range, have a transition temperature as high as 420F. This means that, even though the steel is fully ductile at its operating temperature, as the temperature is lowered during shutdown, it quickly passes into the brittle range. An existing crack or defect could then propagate and cause failure either with or without an impact load. The embrittlement mechanism includes segregation of the responsible impurities along prior austenitic grain boundaries. Temper embrittlement of older equipment is handled by limiting pressurization until the equipment temperature is well above the transition temperature. Temper embrittlement is also reversible. Steel can be deembrittled by heating to above 1100F to 1200F, followed by rapid cooling to room temperature. This is not practical for large pressure vessels in refinery conditions. Of course, embrittlement will return if exposure in the embrittlement range again occurs. The susceptibility of new equipment to temper embrittlement can now be controlled by alloy composition to reduce the content of embrittling impurities. (For more detail, see Section 5.3.) 885F embrittlement occurs after aging of ferritic stainless steels above 12Cr at 700F to 1000F and produces a loss of ambient temperature ductility. This loss of ductility is unrelated to sigma embrittlement. Ductility can be restored by heating to 1200F, followed by rapid cooling.
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4.10.5
Sigma Phase Sigma phase formation occurs when austenitic and other stainless steels with more than 17% chromium are held in the temperature range of 1100F to 1700F for an extended period of time that depends on temperature. Sigma is a hard, brittle, non-magnetic phase containing approximately 50% Cr. Chemically, sigma phase represents an iron-chromium intermetallic compound approximately equivalent to FeCr. In austenitic SS, it forms from residual ferrite. Cold work promotes its formation. There is an increase in the alloy's room temperature tensile strength and hardness, accompanied by a decrease in ductility to the point of brittleness. As a result, cracking is likely to occur during cooling from operating temperatures, handling, and repair welding. Appreciable amounts of sigma phase can also interfere with weld repairs on a component. Nickel promotes the formation of austenite, and chromium promotes the ferrite phase. Therefore, high nickel alloys are immune to sigma formation, and the high chromium alloys are susceptible. The susceptibility and rate of formation of sigma phase in intermediate alloys depend on the ratio of Ni and Cr. During sigma transformation, neighboring areas are depleted of chromium. This can lead to failures along grain boundaries if the material is exposed to corrosive conditions. Sigma is most likely to be found in cast furnace tubes and other cast furnace components. HK cast stainless steel containing 25% Cr and 20% Ni is especially susceptible to sigma phase formation. Heating the embrittled component to between 1800F and 2000F results in dissolving the sigma phase into the austenite matrix and restoring ambient temperature ductility. A more practical means of avoiding sigma is to limit the ferrite content of the stainless steel. To avoid sigma phase embrittlement, an austenitic stainless steel should not have a ferrite content greater than 10%. Austenitic stainless steel welds and corrosion resistant weld overlays may form significant amounts of sigma during fabrication. The austenitic weld deposit problems can also be minimized by limiting ferrite content to a maximum of 10%.
4.10.6
Carburization and Decarburization Carburization is the increase of carbon content in the surface layer of the steel and results from carbon diffusion into the metal during heating in a suitable carbonaceous atmosphere (hydrocarbons, e.g., methane or carbon monoxide). Carburization occurs at temperatures above 1000F. The reverse process, decarburization, can occur in elevated temperature hydrogen (described in Section 4.2) or carbon dioxide. Frequently encountered mixtures of carbon monoxide and carbon dioxide are capable of both carburizing and decarburizing depending on temperature, the ratio of carbon monoxide to carbon dioxide, and the carbon content of the steel. Coke deposits on furnace tubes are the usual source of carbon. Iron sulfide scale is believed to act as a catalyst in the carburization process. Carburization depends on the rate of PAGE 43 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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diffusion of elemental carbon into the metal and increases rapidly with increasing temperature. The increase in carbon content results in an increase in the hardening tendency of ferritic steels. When carburized steel is cooled, a brittle structure can result. The presence of such a hard, brittle structure may result in spalling or cracking. The use of low - carbon grades of stainless steel to prevent sensitization to intergranular corrosion will be of little value if substantial carburization occurs before the alloy is exposed to the conditions causing sensitization and corrosion. Resistance to carburization escalates with increasing chromium content in steel. Decarburization may decrease the endurance limit of steel. 4.10.7 Liquid Metal Embrittlement Liquid metal embrittlement is a form of catastrophic brittle failure of a normally ductile metal caused when in contact with a liquid metal and stressed in tension. In refineries, liquid metal embrittlement has been experienced in copper alloys exposed to mercury and austenitic stainless steels in contact with molten zinc or aluminum. Mercury that is present in some crude oils and subsequent refinery distillation processes can condense and concentrate at low spots in equipment, such as condenser shells. Similarly, the failure of process instruments that use mercury has been known to introduce the liquid metal into refinery streams. Copper alloys, such as used for condenser tubes, when contacted by mercury, are wetted intergranularly and then fracture under relatively low tensile loads. Welding and fire exposure can produce embrittlement from molten zinc from galvanized components and molten aluminum from insulation coverings that are in close contact with austenitic stainless steels. Wetting of the austenitic steel grain boundaries by the zinc or aluminum results in a bond strength reduction and in intergranular cracking. In the case of zinc-rich paints, only those that have metallic zinc powder as a principal component can cause zinc embrittlement of austenitic stainless steels. Paints containing zinc oxide or zinc chromates do not cause cracking. 4.11 References 1. API Publication 941, Steels for Hydrogen Service at Elevated Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants. High Temperature Sulfidic Corrosion in Hydrogen Free Environment, Henry F. McConomy, API 28th Mid-year Meeting, May 1963. New Computer Correlations to Estimate Corrosion of Steels by Refinery Streams Containing Hydrogen Sulfide, A.S. Couper and J.W. Gorman. NACE, March 1970. NACE, Corrosion Data Survey, 1985.
2. 3.
4.
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5.
Corrosion in Petroleum Refining and Petrochemical Operations, J.Gudzeit, R.D. Merrick, L.R. Scharfstein, ASM Metals Handbook, Ninth Edition, Volume 13, Corrosion, 1987. An Exploratory Examination of the Effect of SOHIC Damage on the Fracture Resistance of Carbon Steels, M.S. Cayard, et al., Corrosion 97, Paper 525. Fabrication, Welding and Heat Treatment of Nickel Alloys UNS N08800, N08810, N08811 and N08825, C.S. Tassen et al., Corrosion 96, Paper 601.
6.
7.
5. 5.1
MATERIALS FOR PROCESS UNITS General Selection of materials described in this section should be considered typical and most frequently used rather than exact. Different materials may be required, depending on the particular process conditions.
5.2
Crude Distilling Unit 5.2.1 General Crude oil, as such, is not corrosive to carbon steel. Corrosion problems are created by the following impurities: inorganic salts, sulfur compounds, organic acids (mainly naphthenic acid), and organic chlorides. 1. Inorganic Salts Inorganic salts are present in brine produced with the crude oil or are picked up as a contaminant from tanker ballast. The bulk of the salts present in water are sodium chloride (NaCl), magnesium chloride (MgCl2), and calcium chloride (CaCl2), commonly reflecting the composition of seawater. When crude oil is preheated prior to processing, both MgCl2 and CaCl2 begin to hydrolyze at approximately 250F and above and form hydrogen chloride HCl. The chemical reaction of high temperature hydrolysis is: MgCl2 + H2O 2HCl + MgO or HCl + MgOH - depending on temperature The same is true for CaCl2. NaCl does not hydrolyze to any appreciable extent. HCl vapor thus formed is not corrosive at temperatures above the water dew point. For this reason, there is no corrosive acid attack in the preheat system where no free water is present. In the preflash and atmospheric column, HCl is carried up the column with the hydrocarbon where, being highly water soluble, it dissolves in the condensing water to form hydrochloric acid. This highly corrosive acid can create severe corrosion problems in the top of the column, the overhead line, the overhead exchanger, and condensers. The source of the condensing water can be the crude oil, stripping steam, or desalters. The resulting corrosion reaction with steel is: Fe + 2HCl = FeCl2 + H2 The presence of H2S causes another reaction as follows: PAGE 45 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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FeCl2 + H2S = 2HCl + FeS The formation of HCl thus perpetuates the cycle. Several steps can be taken to reduce the severity of this acid attack on carbon steel: a. b. c. d. e. Desalting. Caustic addition. Overhead pH control. Use of corrosion inhibitors. Water washing.
The primary purpose of a desalter is to reduce the amount of salt in the crude oil. The targeted level is less than 1 lb/1000 bbl (PTB). In addition to salt removal, the desalting process also removes entrained solids, such as sand, salt, rust, and paraffin wax crystals which may be present in the crude. In addition to decreasing the severity of the overhead corrosion problems, the desalting process also decreases plugging and fouling in heaters and heat exchangers. The addition of small amounts of dilute (3% weight) caustic (NaOH) to the desalted crude is often an effective way to reduce the amount of HCl hydrolyzing in the preheaters. The caustic converts the hydrolyzable MgCl2 and CaCl2 to the non-hydrolyzable NaCl, thus reducing the amount of HCl produced. While the results of caustic addition can be quite beneficial, there is a risk of plugging, metal cracking, and catalyst contamination problems in downstream units if it is not controlled properly. The caustic concentration in the crude oil should not exceed 3 PTB or 10 wppm. The desired result of an overhead pH control program is to produce an essentially noncorrosive environment by neutralizing the acidic components in the overhead liquid. This is done by injecting ammonia, an organic neutralizing amine, or a combination of the two. The desired pH control range depends on the concentrations of the various components of the corrosive environment (usually between 5 and 6). Most overhead corrosion control programs include injection of a film forming organic inhibitor as an additional protection. These inhibitors establish a continuously replenished thin film which forms a protective barrier for the metal surface underneath. For maximum results, proper pH control of the system is essential. When fouling with neutralization reaction products becomes a problem, water should be injected, either intermittently or continuously, to dissolve salt deposits. 2. Sulfur Compounds It is difficult to exactly predict the corrosivity of a crude oil based entirely on its sulfur content. Generally, the dividing line between non-corrosive and corrosive is at approximately 0.5% to 0.6% level. The more precise factor is not the total amount of sulfur compounds but rather the
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extent to which these compounds thermally decompose to form H2S, the most corrosive sulfur compound. High temperature sulfur attack is a serious problem in hot portions of the atmospheric column, preflash column, vacuum column, fired heater tubes, hot heat exchangers, and associated piping. The problem is alleviated by the use of proper alloy materials, which will be discussed later. The aqueous phase H2S corrosion and cracking is widespread in predominantly carbon steel equipment. This service may require PWHT and use of HIC resistant steels (see 4.6.2). 3. Organic Acids Many crude oils contain organic acids but seldom do they constitute a serious corrosion problem. Some crudes contain sufficient quantities of naphthenic acid (one of the organic acids) to cause severe problems in those parts of the crude unit operating over 450F. Thus, naphthenic acid attack may occur in the same places as high temperature sulfur attack, such as heater tube outlets, transfer lines, column flash zones, and pumps. The corrosion rate is strongly affected by velocity. The most commonly used material is Type 316 stainless steel which performs well because of its molybdenum content. For better protection, Mo content in 316 stainless steel should be no less than 2.5%. 4. Organic Chlorides Organic chlorides constitute a contaminant in crude oil, often resulting from the carryover of chlorinated solvents which are used in the oil fields. They can also be picked up by the crude during transportation in contaminated tanks or lines. Since organic chlorides are not removed by the desalters, they can decompose in the heaters and cause erratic pH control and accelerated corrosion in the crude unit overhead systems, as well as downstream units. 5.2.2 Material Selection 1. Atmospheric Towers - Carbon Steel Base Metal (From Top of Tower Down) a. Monel clad past dew point, below top reflux but not below 400F (usually 2 - 3 trays) if substantial hydrochloric acid corrosion is expected. 316L clad 450F down (for naphthenic acid protection). 410S clad 500F down (without naphthenic acid). Transition from Monel to stainless clad should be 0.25 inch corrosion allowance carbon steel. Trays same as clad. Trays in carbon steel section should be 410S.
b. c. d. e. 2.
Vacuum Tower - Carbon Steel Base Metal (From Top of Tower Down) a. b. 0.25 inch corrosion allowance to 450F-500F (without naphthenic acid). 316L clad from 450F down (for naphthenic acid protection).
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c. d. 3.
410S clad from 500F down (without naphthenic acid). Trays match clad (410S trays in carbon steel section).
Stripper Towers Stripper towers should be similar to atmospheric tower.
4.
Other Towers Carbon steel with 0.125 inch corrosion allowance, unless estimated corrosion rate exceeds 10 mils per year, such as in hot or aqueous sulfide. If there is a question, specify 0.25 inch corrosion allowance if alloy clad not justified.
5.
Drums Consistent with towers. Gunite lining used where aqueous sulfide considered to be a problem. Monel liners in boot or nozzles are usually used if too small to gunite.
6.
Exchangers a. Tubes (1) (2) (3) b. Carbon steel to 500F. 5Cr-0.5Mo from 500F to 650F. 9Cr or 12Cr above 650F.
Tubesheets, Shell, and Channels (1) Carbon steel to 550F, with 0.25 inch corrosion allowance above 500F or where there is considerable aqueous sulfide. 410S clad above 550F.
(2) c.
Baffles (1) (2) Baffles should match shell. If shell has high corrosion allowance, baffles should also have high corrosion allowance.
7.
Overhead Condensing System a. Air Cooler - Carbon steel for tubes, tubesheets, and headers normally with 0.25 inch corrosion allowance (except tubes). Where considerable hydrochloric acid and/or aqueous sulfide are present, use Monel or Monel lined headers and tubesheets with Monel or 70-30 Cu-Ni tubes. Alternate material for tube: Titanium Grade 2. b. Condensers and Coolers - cooled by fresh water (cooling water in tube side). (1) Tubes - admiralty or 70-30 Cu-Ni if ammonia stress corrosion cracking potential high (e.g., pH greater than 7 in presence of ammonia). Tubesheets - naval brass or Monel lined carbon steel, or carbon steel with heavy corrosion allowance. Channels and floating heads - Monel lined carbon steel or carbon steel with heavy corrosion allowance.
(2)
(3)
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c.
Condensers and Coolers - cooled by seawater (cooling water in tube side). (1) Tubes - aluminum brass or 70-30 Cu-Ni or Titanium Grade 2 if ammonia stress corrosion cracking potential is high. Tubesheets - naval brass or aluminum bronze or Monel lined carbon steel. Channels and floating heads - aluminum bronze or 0.25 inch corrosion allowance carbon steel with an epoxy phenolic coating and galvanic anodes.
(2) (3)
General Note: Alternate materials for tubes are Monel and 904 SS. Carbon steel can be used only when there is very careful cooling water control. 8. Heater Tubes a. Atmospheric. (1) (2) (3) Convection - usually 5Cr-0.5Mo. Radiant - 5Cr-0.5Mo or 9Cr-1Mo with 0.125 inch corrosion allowance. Steam superheaters - dependent on flue gas temperature. At temperatures above 850F, tubes should be 1.25Cr-0.5Mo tubes. Below 850F, tubes should be carbon steel.
b.
Vacuum. (1) (2) (3) Convection - usually 9Cr-1Mo. Radiant - 9Cr-1Mo with 0.125 inch corrosion allowance. Steam superheater - dependent on flue gas temperature. At temperature above 850F, tubes should be 1.25Cr-0.5Mo. Below 850F, tubes should be carbon steel.
c. d.
Other heaters - other heaters are normally carbon steel with 0.125 inch corrosion allowance. General, all heaters - Take potential fuel ash corrosion problems into account when designing fuel oil fired heaters. As a guide, begin to anticipate potential problems on hangers, supports, and baffles with sulfur greater than 2% and vanadium greater than 50 ppm. For remedies, see Section 4.8.
9.
Piping a. Process Piping - Usual Materials Selection (1) Carbon steel to 550F. Corrosion allowance above 500F and where considerable aqueous sulfide is present should be 0.25 inch. 5Cr-0.5Mo from 550F to 650F. 9Cr-1Mo above 650F.
(2) (3) b.
Sour water piping - Past practice has been to use cement lined pipe with small Monel pipe and Monel trimmed carbon steel valves. Carbon steel with 3/16 inch corrosion allowance and 316 SS valve trim has
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been used quite successfully and is much more economical. GEMS J-2D, Table 7, contains available piping material service specifications. c. Atmospheric overhead line - line should be kept above the dew point to permit use of 3/16 inch corrosion allowance carbon steel. Monel can be used after the overhead stream is condensed. Heater transfer lines - atmospheric and vacuum heater transfer lines are usually 9Cr-1Mo unless naphthenic acid is expected to be a problem. Consideration should be given to the use of 316L or 317L if high neutralization number crudes are to be run. Seawater Line (1) (2) Large lines - cement lined steel. Small lines - Monel, plastic (high density polyethelene or equal), or other nonmetallic materials.
d.
e.
10. Pumps In general, impellers should be cast iron or carbon steel with steel cases. Above 550F cases and impellers should be 12Cr or CA6NM (cast 12Cr). Use of cast iron or ductile cast iron should be considered for noncorrosive water services. Seawater pumps should be Ni-resist (ductile austenitic cast iron) or Monel for wetted shafts. 5.3 Hydrotreater - Hydrocracker 5.3.1 General The corrosion problems which should be taken into consideration for hydroprocessing units include high temperature sulfidation, high temperature hydrogen attack, hydrogen cracking, chloride cracking, polythionic acid cracking, aqueous sulfide corrosion, and ammonium hydrosulfide corrosion. Materials for high temperature hydrogen are selected based on Nelson Curves (Figure 1). Based on the recent experience, the Cr content in 1Cr-0.5Mo and 1.25Cr-0.5Mo steels in high temperature hydrogen should be no less than 1.25% to avoid hydrogen attack problems. When temperature exceeds 500F-550F in H2-H2S mixtures, severe corrosion occurs on carbon and low-alloy steels. Before hydrogen enters the process stream, 5Cr-0.5Mo or 9Cr-1Mo can be used. Downstream of the hydrogen injection, 300 series stainless steels are required. Low chrome steels in these conditions require aluminizing to minimize high temperature sulfidation (rapid attack can still occur at breaks in the coating). 5.3.2 Reactors 1. Materials selection for reactors is based on: a. b. c. Resistance to hydrogen attack. Resistance to H2 - H2S corrosion. Notch toughness considerations.
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d.
Strength and fabrication considerations.
Most hydrotreater and hydrocracker reactors are hot shell vessels. The minimum base material for a reactor is determined based on the resistance to hydrogen attack at the process hydrogen partial pressure and temperature. Minimum base materials usually range from 1.25Cr-0.5Mo to 2.25Cr-1Mo. The need for higher alloy corrosion protection by using clad or weld overlay can be estimated by using the Couper curves for H2 - H2S corrosion. (See Figures 4 through 6) In most hydrotreater reactor applications, Type 321 SS clad or Type 347 SS weld overlay is required. The choice of using clad or overlay is usually up to the fabricator. Clad is usually used up to approximately 2.50 inch base metal thickness and overlay above. The decision is made by the fabricator depending on his overlay facilities and the problem of obtaining clad in heavy sections. The notch toughness and fabrication considerations depend on the size and thickness of the reactor. For example, it is often desirable to minimize weight and increase notch toughness by using 2.25Cr-1Mo with a Division 2 design. These considerations usually apply above 2.50 - 3.0 inch thickness. During high temperature service, the reactor base metal may undergo temper embrittlement (see Section 4.10.4) which may cause substantial decrease of notch toughness. To reduce susceptibility and to control temper embrittlement of 2.25Cr-1Mo, the following requirements shall be satisfied. 2. Chemical Limits Requirement a. Reactor plate and forging material chemical limits shall be controlled as follows: J = (Si + Mn) x (P + Sn) x 104 < 100 (with the elements in weight percent) Consideration should be given in relation to the minimum silicon level content to ensure that hot tensile properties are not detrimentally reduced by low silicon content. b. Tramp elements shall be as follows: P = 0.010% MAX Sn = 0.010% MAX Sb = 0.004% MAX As = 0.015% MAX S = 0.010% MAX Cu = 0.200% MAX Ni = 0.200% MAX V = 0.050% MAX P + S = 0.018% MAX c. Weld metal chemical composition should be controlled within the following limits:
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x =
10P + 5Sb + 4Sn + As 100
15
(With the elements in weight PPM.) 3. Additional Notch Toughness Requirement a. Samples representing base metal, weld metal, and heat affected zone should be additionally impact tested after step cooling treatment per the following cycle: (1) (2) (3) (4) (5) (6) (7) b. Hold at 1100F for 1 hour. Cool 10F/hr to 1000F and hold for 15 hours. Cool 10F/hr to 975F and hold for 24 hours. Cool 10F/hr to 925F and hold for 60 hours. Cool 10F/hr to 875F and hold for 100 hours. Cool 50F/hr to 600F. Air cool.
The following 40 ft-lb impact energy transition relationship should be maintained after a step cooling treatment:
To + 3T
Where: To =
Tmin
Temperature at which Charpy V-notch toughness is 40 ft-lb after PWHT and before step cooling. Tsc - To (or temperature shift). Temperature at which Charpy V-notch toughness is 40 ft-lb after PWHT plus step cooling. Minimum metal design temperature.
T Tsc
= =
Tmin
Reactors are designed to ASME Section VIII, Division 1 or Division 2. Division 2 permits higher allowable stresses but specifies more rigorous inspection and stress analysis. 4. Hydrogen Embrittlement Hydrogen embrittlement is also a concern in the reactors of hydroprocessing units. Such reactors operate at high enough temperatures and hydrogen partial pressures to result in a significant concentration of dissolved hydrogen within the walls at operating temperatures. If the reactor walls are thick enough and are cooled rapidly when shutting down, the dissolved hydrogen will not be able to escape from the metal during cooling. The entrapped hydrogen may adversely affect metal mechanical properties and fracture mechanics properties, especially at temperatures above 300F (149C). One concern is that preexisting fabrication flaws or other defects will grow due to hydrogen embrittlement. To avoid this risk, a shutdown procedure may be required to let a significant amount of hydrogen diffuse out of the metal before the reactor is cooled below 300F. This procedure includes an outgassing step that involves holding PAGE 52 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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at high temperatures and low hydrogen partial pressures for particular periods of time as part of the cooling process. Thick-walled reactors in hydrogen service should be inspected with particular care after initial construction and during plant turnarounds to guard against existing defects which might enlarge due to hydrogen embrittlement. 5. Test Blocks Texaco practice for a number of years has been to install test blocks in hydroprocessing reactors (usually two per reactor). Test blocks should be made of the same heats as the reactor materials and should be welded using the same production welding materials and the same welding procedures and NDE methods as for the reactors. If the reactor has an SS weld overlay, the test blocks should be overlaid on all sides with the same overlay. Test blocks are recommended to be installed in the gas phase with the highest temperature. Testing test blocks during reactor operation will determine if the metal has undergone any deterioration. The following tests are usually performed: tensile and impact tests, step cooling tests, and metallography. 5.3.3 Exchangers As a minimum, all exchange equipment that will handle hydrogen should be satisfactory for the process design hydrogen partial pressure and temperature. Materials are also selected on the basis of the estimated corrosion rate from the H2S or H2 - H2S curves. Corrosion rates on the feed side of the reactors should be kept very low to minimize scaling and subsequent reactor pressure drop problems. Heat exchange may be limited on the feed side due to fouling. Antifoulants should be considered if the feed from tankage is used. Tankage feed may contain considerable oxygen that may form long chain polymers on heating. Feed-effluent exchangers are made of materials similar to those used in reactors. Tubes are usually 321 or 347 SS. Materials for exchangers not handling hydrogen are selected on the basis of sulfur corrosion curves and experience. The materials temperature breaks are similar to the crude unit as long as hydrogen is not involved. 5.3.4 Condensers and Coolers Reactor section condensers and coolers are usually carbon steel with a heavy corrosion allowance. The brasses normally used in water service are very vulnerable to the high ammonia concentration. Waterside corrosion problems can be expected, particularly on the reactor effluent coolers, which usually have the cooling water on the shell side. Cooling water velocities that are too low promote serious pitting problems. Most other condensers and coolers can be the same as specified in the crude unit, unless special problems exist.
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5.3.5
Air Coolers Water is usually injected upstream of the reactor effluent air cooler to prevent ammonium bisulfide (NH4HS) (and sometimes ammonium chloride (NH4Cl))deposit formation in piping and tubing. The water solution of NH4HS may be very corrosive towards carbon steel. Corrosion severity has been correlated to a factor Kp, which is defined as the product of mole percent concentrations of ammonia and hydrogen sulfide in the process stream before water injection. Where Kp exceeds 0.05, the process stream velocity in piping (downstream of the water injection point) and in any point of the air cooler must not exceed 20 ft/sec. Water injection rate shall keep NH4HS concentration in water below 2% - 4%. The reactor effluent air cooler is usually high corrosion allowance carbon steel (e.g., 10 gage minimum tubing with 0.25 inch corrosion allowance headers). Alloy tubes at Kp values less than 0.4 may not be justified. Much depends on keeping actual velocities below 20 ft/sec and proper symmetrical design of aircooler inlet and outlet piping. Minimum stream velocity of 10ft/sec should also be maintained to prevent water phase separation and deposit of precipitation which increase corrosion. If Kp exceeds 0.4, alloy tubing (duplex SS, Incoloy, etc.) should be used along with lined tubesheet (in some cases it may be more economical to line the whole header). For alloy tubing, the upper limit of the velocity stream can be raised to 30 ft/sec. Fractionation section air cooled exchangers should be carbon steel, unless very high wet H2S concentrations exist. Then the use of a filming amine inhibitor or a corrosion resistant alloy should be considered.
5.3.6
Towers Towers should consist of carbon steel with a 0.125 inch corrosion allowance, unless there is corrosive hot or aqueous H2S. In hot service, 410S SS cladding may be required. Aqueous H2S usually needs a 0.25 inch corrosion allowance.
5.3.7
Drums Materials for drums are consistent with towers, except that gunite is used with a 0.125 inch corrosion allowance or 0.25 inch corrosion allowance in aqueous H2S. The minimum material may be set by hydrogen partial pressure.
5.3.8
Pumps Pumps should consist of cast iron or carbon steel impellers with steel cases. Above 450F-550F, 12Cr or CA6NM cases and impellers should be used. Cast or ductile iron should be considered for water service.
5.3.9
Sour Water Piping See 5.2.2, paragraph 9. Monel shall not be used in high ammonia concentrations.
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5.3.10
Heaters Charge heaters with H2 require austenitic stainless steel tubes, Type 347, unless concentration of H2S is very low. Type 321 SS has also been used. Stainless steel return bends should be wrought rather than cast both to obtain superior quality and to avoid sigma phase embrittlement (see 4.10.5). Fireside deposit corrosion problems must be considered when selecting tube materials. Without H2 in the heater, 9Cr-1Mo tubes are used. Most fractionation heaters can be carbon steel, unless considerable H2S or high outlet temperatures are involved. 5Cr-0.5Mo may be required for H2S. A lower Cr alloy may be required for strength at elevated temperature.
5.3.11
Piping Piping is selected per hydrogen attack and H2S or H2 - H2S curves. Materials should be used that minimize scaling in the reactor feed circuit. Much of the reactor circuit is austenitic stainless steel. Cr-Mo steels may be satisfactory at temperatures above 500F - 550F upstream of hydrogen injection. For the guidelines on the reactor effluent piping downstream of the water injection point see 5.3.5. If this piping is subject to high corrosion rates and premature failure despite taking the recommended measures (proper process stream velocity, etc.), the use of a corrosion resistant alloy (e.g., Incoloy 825) should be considered. If corrosion inhibitors and antifoulants are used, careful selection is required to protect the water separation characteristics of products, such as Avjet.
5.4
Catalytic Reforming Units 5.4.1 General Materials selection in catalytic reforming units is almost entirely based on considerations of resistance to high temperature hydrogen attack. 5.4.2 Reactors Hotwall reactors are 1.25Cr-0.5Mo, which has adequate strength at design temperatures and is resistant to hydrogen attack. Coldwall reactors are carbon steel with 1.25-0.5Mo nozzles. Stacked reactors for continuous regeneration are 1.25Cr-0.5Mo. Internals are usually 410 or 316 stainless steel. Newer units use 316, which is not vulnerable to the embrittlement problems of 410. Because of the high chloride levels in the catalyst, consideration must be given to the potential for chloride stress corrosion cracking, particularly during downtimes. 5.4.3 Exchangers New combined feed exchangers are usually true countercurrent flow. Material requirements are set by the hydrogen partial pressure. Tubes, channels, and shells are usually 1.25Cr-0.5Mo. When specifying materials, it should be noted that it is nearly impossible to accurately predict temperatures in an exchanger. PAGE 55 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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Parts, such as shells, should be of one material or the material breaks should be conservative. True countercurrent flow bundles should not be used for high maintenance exchangers, such as unifiner feed/effluent exchangers, because they are difficult to assemble. Since sulfur is not involved in the platforming section of the CRU, all other exchangers can usually be carbon steel, as long as there is no potential for hydrogen attack. 5.4.4 Air Cooled Exchangers All air cooled exchangers are usually carbon steel. 5.4.5 Condensers - Coolers All condensers and coolers can be standard admiralty, except where there may be high ammonia concentrations. Admiralty can be used in many of the condensers and coolers if suitable handling procedures are used before opening. The effluent cooling train is the only area subject to problems. Admiralty or aluminum brass bundles should be water washed before being opened to avoid ammonia cracking (see Section 4.6.7). 5.4.6 Piping The reactor section piping must meet hydrogen attack criteria. The hot section will usually be 1.25Cr-0.5Mo. Most other piping can be carbon steel. 5.4.7 Pumps Pumps should have a steel case and cast iron or carbon steel impellers to 450F - 550F and 12Cr or CA6NM above. 5.4.8 Heaters The platformer charge and intermediate heaters use 1.25Cr-0.5Mo headers and either 2.25Cr-1Mo or 9Cr-1Mo tubes. Although the 2.25Cr-1Mo has been used successfully for many years, new units need the increased oxidation resistance of 9Cr-1Mo because of a higher flux rate and higher metal skin temperature. The latter can be above 1150F at the end of runs. Other heaters can usually have carbon steel tubes. 5.4.9 Recycle Compressor Recycle compressors are subject to corrosion of the rotating element by chlorides and have the potential for hydrogen embrittlement. The machines are usually washed before opening, which cleans out the soluble chloride deposits. Welding and heat treating restrictions are applied to the compressors to minimize potential cracking problems. Suction lines should be traced or jacketed to minimize moisture during service. Minimizing moisture should minimize corrosion and deposits. Suction knockout drums and demisters should be specified. 5.4.10 Special Corrosion Problems Corrosion is usually at a minimum during operation as the higher temperatures do not allow condensation of corrosive compounds. But the feed may contain some hydrogen and the
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catalyst contains chlorides. Resulting from hydrogen interaction with these substances, hydrogen chloride gas or ammonia may form. On cooling and condensation, when component is shutdown, formation of corrosive hydrochloric acid or ammonium chloride may occur. This may plug the air cooled reactor effluent condenser and cause deposit problems in the recycle compressor. To prevent this, the following equipment is water washed: 1. 2. 3. 4. Effluent coolers. Flash drum separators. Recycle compressors. Strippers and associated piping.
A 5 weight % sodium bicarbonate solution is a good choice for the washing medium as the slight alkalinity overcomes the acid hydrolysis of ammonium chloride when the water is introduced into previously dry equipment. In order to remove hydrogen chloride from recycle gases, HCl traps may be installed in the lines leading from the separators. 5.5 Fluid Catalytic Cracking Units 5.5.1 General The feed system on an FCCU is similar to a crude unit atmospheric preheat section. Somewhat less sulfur corrosion should be expected, since at least some of the sulfur compounds are thermally converted to H2S in the crude unit or in feed hydrotreaters, if used. The material selection is based on having at least 1% sulfur in the feed. The feed heater uses either 5Cr-0.5Mo or 9Cr-1Mo tubes to minimize sulfur corrosion and give higher strength and oxidation resistance. Exchanger tubes go from carbon steel at 500F to 5Cr-0.5Mo, with 12Cr over 650F. Piping above 550F should be 5Cr-0.5Mo from the corrosion and erosion standpoint. Some units have 9Cr-1Mo piping above 650F in both the fresh feed and recycle circuits. 5.5.2 Reactor Section Many of the older units have carbon steel hotwall reactors clad with 410 stainless steel. Over the years, the cladding has corroded or eroded, and refractory linings have been required. Current practice is to use a cold shell design with refractory lining and a carbon steel shell. A 4 to 5 inch layer of medium weight refractory, such as A.P. Green Greencast-45LGR (or equal), is generally specified. If they are large enough (greater than approximately 30 inches), fresh feed risers are refractory lined. Single layer vibration cast refractory is preferred for riser lines to provide both erosion protection and insulation. A 4 to 5 inch layer of Premier AR-400 (or equal) refractory is typical. Vibration cast linings generally contain 3 weight % of SS needles for increased resistance to cracking. If the lines are smaller, hardfacing, such as chromium carbide, cobalt based alloys (Stellites), nickel - chrome, boron alloy (Colmonoy), or PAGE 57 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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equal, are used. Risers can be carbon steel if kept below approximately 750F by the refractory and internal insulation. Higher temperature hardfaced lines need to be 1.25Cr-0.5Mo from strength considerations. All catalyst handling lines are refractory lined or hardfaced, depending on size to minimize erosion problems. The reactor internals, such as cyclones, are carbon steel or low alloy, depending on the strength required, and are refractory lined for erosion protection. Above 850F, potential of carbon steel loss of strength, resulting from long-term graphitization, should be considered. Nevertheless, current practice is to use carbon steel for all reactor internals, such as cyclones, stripper baffles, steam distributors, at design temperatures up to 1050F. Items requiring high strength, such as vessel lugs, supports, or cyclone hanger rods, can be of low alloy or stainless steel. General practice is to avoid the use of austenitic stainless steels for reactor internals. If stainless steel is used because of higher sulfur and temperature, stabilized grades, such as 321 SS or 347 SS, should be used to minimize potential intergranular cracking problems due to polythionic acid formation during downperiods. 5.5.3 Regenerator Regenerators are refractory lined cold shell carbon steel vessels. With regeneration temperatures rising from the 1100F range to 1250F and above, internals, such as cyclones and their support systems, have gone from carbon steel to 2.25Cr-1Mo and finally to Type 304H stainless steel. 2.25Cr-1Mo cyclones carburize at temperatures over 1200F and are very brittle at room temperature. New cyclone installations have been with Type 304H SS. Types 321 SS and 347 SS are not used because of much lower allowable stress levels. Although Type 304H sensitizes, downperiod intergranular cracking conditions are not as favorable as in the reactor. After long exposure to high temperature, desensitization of 304H SS is supposed to occur. It can sensitize again during slow shutdown cooling, but experience has shown that polythionic acid cracking failures in regenerator are rare. It is often desirable to install refractory linings on the outside of regenerator internals, in addition to any refractory inside, if exposure to turbulent catalyst flow inside the regenerator occurs. If air distribution rings are employed, external refractory linings are also common. Much of the regenerator internals subject to erosion are lined using an intermediate density or phosphate-bonded castable. Such linings should contain metal fiber for reinforcement and are generally 1 inch (25 mm) to 2 inch (50 mm) thick. Many of the problems experienced with austenitic stainless steel cyclone systems are due to the higher thermal expansion and to distortion problems. Use of spray or quench water to the cyclones during temperature excursions is no longer recommended due to damage caused by spray impingement on hot surfaces.
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Design at over 1300F requires a detailed investigation to recommend the most suitable materials. 2.25Cr-1Mo is usually satisfactory for internals in the lower part of the regenerator, except if temperatures exceed 1300F. 5.5.4 Slide Valves Older slide valve designs were generally of hot wall construction with internal refractory lining or hard facing for erosion protection only. Slide valves designed to approximately 1250F were typically 1.25Cr-0.5Mo or 2.25Cr-1Mo at the higher temperature end. Above 1250F, austenitic stainless valves were used. These were, however, subject to polythionic acid attack during down periods. Current practice is to use cold wall slide valve designs in both reactor and regenerator service. Cold wall designs typically have carbon steel valve bodies with vibration cast refractory for insulation and erosion protection. Valve internals are generally low alloy or stainless steel depending on temperature. 5.5.5 Major Lines The reactor overhead line that carries cracked gas from the reactor to the main fractionator is typically unlined 1.25Cr-0.5Mo. Materials selection is based primarily on the need for strength and resistance to high temperature graphitization. Localized attack by high temperature H2S is possible at cool spots where heat is drawn away by external supports (e.g., a protective coke barrier does not form at the lower temperature). However, the potential for H2S attack in this environment is not a strong driver for upgrading to more sulfidation resistant alloys. Although normally solved through design and not materials upgrading, fatigue cracking has occurred in reactor overhead lines, especially at miters. The source of the stress is the differential thermal growth between the reactor overhead and the fractionator inlet nozzle that can place high strains on the piping each time the reactor is cycled. With todays high temperature regenerators, flue gas exits the regenerator at 1250 F (675 C) to 1425 F (775 C). Erosion from catalyst fines, oxidation resistance, carburization resistance, and the need for high temperature strength are the primary concerns. In flue gas ducts, erosion is more of a problem at elbows than in straight runs. Erosion is particularly severe in, and just downstream of, restriction orifices and the slide valve. Piping materials for the regenerator overhead line are typically refractory lined carbon steel. When a power recovery turbine in used, inlet piping is typically uninsulated 3xx series stainless steel to avoid refractory particles entering the turbine. Catalyst transfer piping is usually constructed of carbon or low alloy (5Cr-0.5Mo, 9Cr-1Mo) steel with an internal refractory lining. Previously, a dual-layer refractory lining was used, supported by hexmesh. As refractory technology improved, the refractory of choice has become the single layer, vibration cast, heavy weight refractory, supported by vee
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studs. The quality of this lining has been further improved by reinforcement with stainless steel (Type 304) needles. Another problem is the failure of several large diameter expansion joint bellows in various lines. The standard bellows material has been 321 SS, which is very susceptible to chloride stress corrosion cracking when exposed below the dew point. There are sufficient chlorides available to cause failures very rapidly. Bellows with much better chloride stress corrosion cracking resistance, such as Inconel 625 and Incoloy 825, are now being recommended in some services. 5.5.6 Fractionation and Gas Recovery The main fractionator is handled similarly to a crude unit atmospheric tower with 410S clad part way up the tower to approximately 500F. The gas recovery section handles large amounts of H2S and NH3 and should have full protection from sulfide stress corrosion cracking and hydrogen embrittlement and/or blistering. All equipment exposed to wet H2S should be stress relieved with hardness after PWHT that does not exceed 200 Brinell. Critical problem areas are the overhead systems of the fractionator, depropanizer, absorber - deethanizer, and around the compressor. For some extreme cases, including previous experience with severe hydrogen blistering, the use of HIC resistant steel (see Section 4.6.2) should be considered. Brinell hardness of piping welds, base metal, and heat affected zone in wet H2S service is limited with 200 Brinell. Sulfur corrosion rates are usually not as high as on a crude unit. 5Cr-0.5Mo lines are used over 550F, although some 9Cr-1Mo has been used at higher temperatures. Low temperature problems with deposit buildup around compressors and cyanide related corrosion problems around the absorber must be recognized. Copper base alloys and Monel are usually subject to very high corrosion rates and in some cases to stress corrosion cracking because of the high ammonia concentrations. The compressor can usually consist of standard materials from the corrosion standpoint, but the 90,000 psi maximum yield criteria must be used. Compressor material restrictions are specified in GEMS. More specific recommendations on cyclones, refractory, and slide valves are specified in FCCU cyclone GEMS and in Texaco slide valve purchase recommendations. 5.6 Alkylation Units 5.6.1 Reactor Section Texaco alkylation units use 98% H2SO4 as the catalyst. The reaction is run in the contactors at low (20F - 50F) temperature, which allows considerable carbon steel to be used. Due to the below ambient temperature, carbon steel with improved notch toughness, such as A 516, is required, particularly for heavier walled vessels. Carbon steel piping is adequate from the corrosion standpoint around the contactors if the velocities are low (2 ft/sec range). Welds in contact with sulfuric acid in some cases are post weld heat treated to minimize hydrogen cracking and/or preferential corrosion of weld metal or heat affected zones. Cold worked metal (usually PAGE 60 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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bends) is also often stress relieved. Weld root beads are often made using gas tungsten arc welding to avoid weld penetration into the line to minimize turbulence that can substantially increase corrosion rates in sulfuric acid. At higher velocities or in turbulent areas, Carpenter 20Cb3 is used. Alloy 20 (the cast equivalent of Carpenter 20Cb3) is commonly used for acid pumps. Acid pump suction and discharge lines may need to be 304 or 316 SS in highly turbulent areas for the first few feet. Vitrified tile is used for acid drain lines. Valves in the reaction section are commonly carbon steel with Alloy 20 trim or all Alloy 20. The contactors are very specialized reactors. Many of the lines in turbulent areas are Carpenter 20Cb3. The impeller is usually Ni-resist, which is a nickel austenitic cast iron. The contactors have a 0.125 inch corrosion allowance. The large refrigeration bundle in the contactor has had erosion problems on the contactor side in the area around the tube supports. 5.6.2 Fractionation Section The rest of the unit is carbon steel, usually with 0.125 inch corrosion allowance. There are a few problem areas in the fractionation section. Potential problems from caustic carryover during neutralizing must be considered in specifying towers and reboilers. Unless the caustic is completely washed out, it can concentrate and cause stress corrosion cracking problems. If carryover is a possibility, equipment should be stress relieved. Depending on the specific fractionating scheme, some tower overhead systems, such as the deisobutanizer and depropanizer, can run at low pHs due to sulfur ester breakdown. Corrosion in the tray and overhead condenser or cooler can result. Many of the upper trays in these towers have been replaced with austenitic stainless steel. Inhibitors have been used in the overhead systems but can be troublesome because of the difficulty of keeping them in solution in the light ends being processed. Care must be taken to control and minimize any ammonia injection to raise the overhead pHs, since severe corrosion and stress corrosion cracking of admiralty or other copper based alloy condensers can result. Some of the older units have had problems with inadequate acid neutralizing. 5.6.3 Compressor The compressor can consist of standard materials, except for the hardness, yield strength, and heat treating restrictions specified in GEMS. 5.7 Gasification Units 5.7.1 General The specific materials selected for gasification units will depend on process design. In refineries, gasification units are used for hydrogen generation. The same units can be used to
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make petrochemical feedstocks, and the produced syngas can also be used for power generation in a combustion turbine. 5.7.2 Oxygen System Carbon steel piping is used from the GSU (Gas Separation Unit) to the process unit boundary. Carbon steel piping is not recommended within the gasification unit battery limit because of the fire hazard. Carbon steel must be meticulously cleaned and always be under a nitrogen blanket when not in service. Since the oxygen piping around the feed injector will be open to atmosphere periodically, carbon steel piping is not practical. All process piping in contact with oxygen within the unit must be 304L SS as a minimum. Monel 400 or Inconel 600 must be used as a fire break within approximately 25 feet of the gasifier reactor. The normal location of this piping spec break is upstream of the oxygen flow control valve and this 25 foot section of piping will terminate at the process feed injector. Monel valve bodies should not be used for the steam purge valves into the oxygen piping as valve body distortion has occurred in high temperature steam service. For high temperature steam purge valves, Inconel 600 is the recommended material. The Compressed Gas Association Pamphlet G-4.4 should be consulted for an overview of oxygen service materials and cleaning requirements. However, the copper base alloys for valve trim, as recommended in this pamphlet, will not be used. Copper base alloy valve trim will experience scouring and valve leakage. 5.7.3 Charge Oil System Materials for the charge oil will depend on the temperature and the sulfur content in the oil. Carbon steel will be used below 550F. Usually, 5Cr-0.5Mo or 9Cr-1Mo will be required at higher temperatures. 5.7.4 Coke Slurry System Erosion of piping in the slurry system will be a problem. Velocity should be designed below 3 feet per second by pipe sizing. Piping configuration will use long radius bends, laterals, and special wear pieces (i.e., basalt lining around pump discharge, mag meters, and other high velocity zones). Pipe should be XXS or schedule 160 carbon steel as a minimum. 5.7.5 Steam System Whenever possible, plant steam will be used, as this eliminates the need for onsite water treating and steam generation. If a waste heat boiler is specified in the process design, the unit will have fire tubes with the steam generated on the shell side.
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The materials for the tubes will be dependent on the metal temperature and composition of the syngas. Usually 1.25Cr-0.5Mo or 2.25Cr-1Mo steels have been adequate. The face of the tube sheet will be protected with a high alumina refractory ramming mix or with specially cast alumina bricks. The tube entrance will be water cooled because of the high heat flux. Several plants have encountered problems with overheating at the tube entrance from high heat flux due to low cooling water flow, which leads to carburization and metal dusting in CO/CH4 rich syngas. The shell side of the waste heat boiler will be carbon steel. 5.7.6 Gasifier Section The gasifier vessel and quench chamber will be 1.25Cr-0.5Mo for high temperature strength and resistance to hydrogen attack. The Nelson curves (API RP 941) will be followed in selecting the gasifier shell material. The gasifier vessel will be internally lined with refractory brick. The corrosion allowance on the shell will be 0.25 inch to accommodate areas of the shell behind the refractory where dewpoint corrosion may occur. This is especially common around the thermocouple nozzles. The exterior of the gasifier will not be insulated. Thermocouple nozzles should be insulated to prevent dew point corrosion inside the nozzle necks. The quench chamber will be clad with 316L SS. Incoloy 825 may be considered where the chlorides in the quench chamber are exceptionally high (i.e., over 1,000 ppm). Formic acid forms during gasification. Therefore, the quench chamber and internals will require materials that are resistant to organic acids. The internals will usually match the clad material, except that Incoloy 825 is required for the quench ring and dip tube where alternate wetting and drying will build a salty ash layer which may stress corrosion crack stainless steels. The draft tube is usually 316L SS as are most of the other internals in the quench chamber. The baffles and gussets in the overhead of the quench chamber are 1.25Cr-0.5Mo steel with a 0.25 inch corrosion allowance on each side. The process burner will be 347 SS for the charge oil components and Incoloy 825 for any parts in contact with oxygen slurry. Inconel 600 components have failed due to polythionic acid stress corrosion cracking in sulfidic corrosion service and therefore should be avoided. Inconel 625 can be used as an alternative to Incoloy 825. Natural gas feed injectors made of Incoloy 800H have experienced severe metal dusting in preheated gas feed at 1100 F. Inconel 600 has worked well in this application. The feed injector main flange will be 1.25Cr-0.5Mo steel to match the gasifier vessel. Cooling water piping above the feed injector flange will be XXS or schedule 160 1.25Cr-0.5Mo alloy steel to the control valve. Carbon steel will be used for the remainder of the cooling water piping. The feed injector cooling water piping tank will be carbon steel with an epoxy liner. As an alternative, carbon steel with a 0.12 inch
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corrosion allowance may be used for the tank provided a corrosion inhibitor is used in the cooling water. 5.7.7 Syngas Scrubbing Section The gas outlet line to the carbon scrubber is carbon steel with 0.25 inch corrosion allowance provided the gas outlet temperature is below 450 F. At higher gas outlets, 25Cr-0.5Mo low alloy steel will be required to prevent hydrogen attack per the Nelson curves in API RP 941. Full heat conservation will be applied to the gas outlet to prevent dewpoint corrosion. The syngas scrubber will be carbon steel or 1.25Cr-0.5Mo low alloy steel per API RP 941. The syngas scrubber will be post weld heat treated for sour service. A 0.25 inch corrosion allowance will be used where the bottoms scrubber water has a pH of 5.5 or higher. For lower pH values, the syngas scrubber should be clad with 316L SS. The internals and trays in the syngas scrubber will be 316L SS. 5.7.8 Water System The water system is characterized by chlorides, low pH due to formic acid, and solids which accelerate erosion of piping and valves. The soot water produced with natural gas or liquid feed to the gasifier is not erosive due to the soft nature of the soot. For petroleum coke gasification, erosion is not considered a serious problem in the slag, and black water water service with an experienced piping design which limits the velocity by proper line sizing, etc. Black water piping will experience erosion around control valves and pump discharge where the velocity is very high. At these locations, special wear pieces can be fabricated or an extra erosion allowance can be applied. The preferred piping for black water and slag is carbon steel with a large corrosion allowance. Even if the velocity is not high, erosion/corrosion on the carbon steel will still require a good corrosion allowance of 0.25 inch minimum. Where the pH of the black water is low from formate and insufficient ammonia production, alloy piping must be considered. A pH of 5.5 is the lowest that can be tolerated on carbon steel for the high pressure systems and this must be frequently monitored for wall thickness. For the low pressure slag piping downstream of the lockhopper, a lower pH could be tolerated on the carbon steel with little consequence in the event of a piping leak. If the pH of the black water is below 5.5, then 316L SS can be used for low chloride conditions. The 316L grade is selected for corrosion resistance to the organic acid. The 316L can be used for chloride levels up to 150 ppm provided that there are no zones where the chloride salts will concentrate by wetting and drying. This did occur at one plant in a heat exchanger bundle. Stress corrosion cracking (SCC) was also experienced in 304 and 316 SS U bend corrosion coupons in plant black water service where alternate wetting and drying occurred.
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If the pH is low and the chlorides are high, then this becomes the case where the duplex stainless steel or Incoloy 825 piping must be used. Duplex SS piping will be alloy UNS S31803 or S32750 with the lowest installed cost being the major consideration. Only highly experienced duplex SS piping fabricators should be selected. For valve bodies in high chloride service, carbon steel weld overlayed with 316L weld metal or SS casting grade CF-8M (316 SS) are utilized. The casting grade CF-8M will have sufficient residual ferrite to resist SCC. Pump casings can also be martensitic stainless steel grade CA6NM where increased erosion resistance is desired. The casting grade CA6NM will be given the heat treatment called for in NACE MR0175 for resistance to sulfide stress corrosion cracking. Grey water piping will experience erosion around control valves and pump discharge where the velocity is very high, especially where flashing occurs. At these locations, special wear pieces can be fabricated or an extra erosion allowance can be applied. For ball valve trim, 316 SS with a nickel boron diffusion coating has performed well. High pressure letdown valves at the flash drum will be angle valve designs with tungsten carbide trim. The preferred piping for grey water is carbon steel with a large corrosion/erosion allowance of 0.25 inch minimum. Alloy piping in grey water should not be required with ammonia recycle from condensate with the resulting subsequent elevation in system pH. Low pressure grey water pumps should be Ni-hard, abrasion resistant cast iron, ASTM A 532 Class III. 5.7.9 Trim Cooler and Condensate Strippers The line coming to the trim cooler will be carbon steel with a heavy corrosion allowance of 0.25 inch. The trim cooler will be carbon steel post weld heat treated for wet H2S service with a 0.25 inch corrosion allowance. Tubes for the trim cooler will be 304 or 316 SS and it is noted that the pH of the condensate in the tubes should be used to select the tube material. For pH below 4.5, 316 SS should be selected for its superior corrosion performance in carbonic acid. The trim cooler KO drum will be carbon steel with 304L SS cladding. The trim cooler KO drum pump around will be 304L or 316L SS piping with a CF-8M pump case and impeller. Carbon steel piping can be considered for the pump around if the pH is above 5.5 and the corrosion allowance should be a minimum of 0.25 inch. The trim cooler KO drum bottoms piping and transfer piping to the condensate stripper will be carbon steel with 0.25 inch corrosion allowance. The condensate stripper feed product exchanger shell is carbon steel with a 0.25 inch corrosion allowance and PWHT for wet H2S service. The tubes will be 316 SS (expect 50 ppm level of HCN in the tubes). The condensate stripper vessel is carbon steel post weld heat treated for wet H2S service. It will have a 0.125 inch corrosion allowance and will be internally lined with acid resistant concrete (i.e., Resco FA-22 or equal). Trays and tray supports are 316L SS and packing will be 316 SS. The reboiler is carbon steel with carbon steel tubes and carbon steel piping. The tube side of the reboiler is PWHT for wet H2S service. PAGE 65 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT
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The pump around piping is carbon steel with 0.25 corrosion allowance. Stainless steel Type 316L should be considered for the pump around piping downstream of the pump to the inlet of the condenser where the velocity is higher. The pump material is recommended in Alloy 20 (casting grade CN-7M) because of the velocity and cyanides. The condenser tubes are titanium grade 2 where the cyanide levels and velocity are high (expect 150 ppm levels of HCN). The bottoms pump is carbon steel with a Ni-resist (ASTM A 439) impeller and the bottoms piping is carbon steel with 3 mm (0.118 inch) corrosion allowance. Where the stripped condensate bottoms has an additional bottoms cooler, the shell will be post weld heat treated carbon steel and the tubes will be carbon steel. 5.7.10 Gas Clean Up System Acid gases, such as H2S and CO2, are removed in sour gas treating units. Selection of materials will follow the guidelines in the section concerning these units. 5.8 Delayed Coking Units 5.8.1 Coke Drums Coke drums have been made of carbon steel, Carbon - 0.5Mo, and 1Cr-0.5Mo. Bulging and subsequent cracking have been a continuing problem with many drums. Drums have been clad with 405 but 410S is preferred. The clad is required to minimize sulfur corrosion. Since the drums operate in the 850F - 900F temperature range, elevated temperature strength and resistance to microstructural change is desirable. Carbon steel drums have relatively poor strength and have a history of bulging problems. Carbon - 0.5Mo has good strength but can suffer a severe loss in notch toughness. The decrease in notch toughness makes carbon - 0.5Mo drums susceptible to cracking problems. 1Cr-0.5Mo has good strength and does not appear to suffer the severe toughness loss experienced by carbon - 0.5Mo. Current material recommendations are for 1Cr-0.5Mo clad with 410S for corrosion protection. The frequent thermal cycles experienced by the coke drums often result in fatigue failure. Typically, coke drums are operated until fatigue cracks in the shell and nozzles increase to a point to be considered unsafe, or the bulging and distortion are so severe that the drums are considered structurally unsound, or the distortion is so severe that the piping can no longer be connected to the drums because of misalignment. 5.8.2 Coking Heater Due to high outlet temperature and need for elevated temperature strength and resistance to oxidation and sulfidation, 9Cr-1Mo is used for heater tubes.
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5.8.3
Fractionator The fractionator is handled as a crude unit atmospheric tower. Coker stocks are expected to be high sulfur. 410S clad is required in areas operating above 500F. A coker may process crude, so consideration must be given to naphthenic acid problems. Many coker charge stocks have high nitrogen contents, so careful material selection is required, particularly when Monel or copper base alloys are considered in the fractionator overhead and gas compression systems (because of potential for ammonia formation).
5.8.4
Towers Towers vary on a coker, depending on individual plant requirements. Use of carbon steel with a 0.125 inch corrosion allowance where the H2S is low and a 0.25 inch corrosive allowance where H2S concentrates is satisfactory. Most towers, other than the fractionator, are not hot enough to require clad. Clad protection would be required above 500F for sulfur corrosion or above 450F if naphthenic acid problems are a possibility.
5.8.5
Drums Carbon steel with 0.125 inch corrosion allowance is satisfactory for areas below 500F and low H2S. Carbon steel with a 0.25 inch corrosion allowance or 0.125 inch corrosion allowance plus gunite is used for wet high H2S.
5.8.6
Piping Hot piping around the coker heater and coke drums to the fractionator is usually 9Cr-1Mo. Piping off the fractionator follows the same material temperature breaks as for the crude unit. That is, carbon steel to 550F, 5Cr-0.5Mo to 650F, and 9Cr-1Mo above 650F. Most of the sulfur left will be very thermostable after exposure to coking conditions. The high corrosion rates that might be predicted for either 5 or 9Cr should not be expected, because most of the sulfur compounds that would form H2S thermally have been removed. Careful use of Monel is required because of possibility of high ammonia concentrations. 0.25 inch corrosion allowance carbon steel piping is usually satisfactory for wet, high H2S areas.
5.8.7
Exchangers Material selection depends on the unit configuration, but sulfide corrosion problems usually set the exchanger metallurgy. As a generalization, exchanger materials selected for crude units are satisfactory.
5.8.8
Condensers - Coolers The standard admiralty condenser or cooler is satisfactory except where high pHs resulting from high nitrogen feed and ammonia formation are present. Water draw pHs above 8 caused by ammonia can cause high corrosion rates (and in some cases stress corrosion cracking) on admiralty and other copper alloys. Carbon steel may be more satisfactory from the process side if the plant can accept it on the water side.
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5.8.9
Air Cooled Exchangers The basic air cooled exchanger is carbon steel. Areas with high H2S require thicker tubes and 0.25 inch corrosion allowance headers. 70-30 Cu-Ni can be used in high H2S areas only if the nitrogen content of the feed is low. This is particularly true of the fractionator overhead and gas compression system.
5.8.10
Compressor The coker gas compressor handles high H2S and usually high ammonia gas. All precautions to prevent sulfide cracking problems must be taken. These precautions include welding and hardness, yield strength, and heat treating restrictions.
5.9
Sour Water Treating Sour water stripping units have been used for many years to minimize the H2S and NH3 released in effluent water. Sour water originates from accumulator, reflux, and knockout drums at various refining units, including crude units, catalytic cracking, hydrocracking, hydrotreating, and reforming units. Consequently, potential corrosive agents include hydrogen sulfide, ammonia, chlorides, cyanides, mercaptans, and phenolics. Due to increased pollution requirements, these units have been modified to more effectively strip waste water. The result of the increased stripping is that corrosion problems have increased. Most of Texaco's new or modified units are non-acidified with overhead and/or reflux condensing. The major problem areas in these units are the overhead and reflux condensers, with some problems in the feed bottoms exchangers. The overhead and/or reflux condensers are usually air cooled to minimize water usage. Service experience with the new designs verifies the potential overhead system problems in terms of corrosion and hydrogen cracking. Duplex stainless steels, such as 3RE60, 2205, or 2507, and in some cases titanium and aluminum alloys, are being used for overhead or reflux condensers tubes in an attempt to minimize corrosion and the probability of chloride stress corrosion cracking. The corrosion problem is primarily due to ammonium hydrosulfides. Because of the high ammonia concentration, copper base alloys and Monel cannot be successfully used. Lines are usually cement lined, subject to size restrictions and/or limitations. A 0.25 inch corrosion allowance is used for small lines. The stripper towers are generally made of carbon steel with heavy corrosion allowance. The internals are carbon steel, 316 SS, or aluminum, depending on corrosion experience. Exposed internals and nozzle liners are 316 or 316L if welded. Feed bottoms exchangers are carbon steel to approximately 180F. Above 180F, tubes are the duplex SS described previously. Feed and bottoms pumps are steel, ductile iron, or Ni-resist. Overhead and/or reflux air coolers have 316L lined headers and tube sheets with the above duplex SS tubes. Reflux pumps are CF-8M, the cast equivalent of Type 316.
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If significant problems develop with the present stainless steel shell and tube and air cooled exchangers, titanium may be considered. All unprotected carbon steel equipment in sour water service should be post weld heat treated per GEMS G-7M to avoid hydrogen stress cracking. In some extreme cases, HIC resistant steels (see Section 4.6.2) may be used. Water soluble filming amine corrosion inhibitors can be injected into the overhead line to help control both corrosion and hydrogen damage. 5.10 Sour Gas Treating Units 5.10.1 General Most of the sour gas treating units in refineries use MEA, DEA, DGA, or MDEA (monoethanolamine, diethanolamine, diglycolamine, or metyldiethanolamine). The problem areas are around the regenerator where the H2S and CO2 are stripped from the solvent. Some problems have occurred in the feed line to the regenerator where the pressure on the rich amine is reduced ahead of the tower. The pressure reduction may cause flashing and increased corrosion rates. Most of the unit is carbon steel. The regenerator and hot lines and overhead line should have a heavy corrosion allowance. The regenerator reboiler usually has 410 SS tubes. The reclaimer (if used) has austenitic stainless steel tubes. In several cases, pitting on 410 SS reboiler tubes has been observed, and they were replaced with austenitic SS. The corrosion rate depends on the metal skin temperature (problems arise above 300F steam temperature) and the solution loading. The amine solution can crack carbon steel, so all lines, towers, exchangers, drums and other equipment, and piping in rich amine or lean amine (but not fresh amine) are post weld heat treated. Some serious corrosion problems may exist in regenerator overhead system. Currently, duplex SS tubes are recommended for regenerator overhead condensers. Regenerator overhead corrosion can be minimized by operating the regenerator such that 0.5% amine is taken overhead. Depending on solution loading and temperature, some plants have had apparent success with titanium in both reboilers and water cooled overhead condensers, where other materials had failed. Many of the new units have air cooled overhead condensers. Aluminum has worked reasonably well but is vulnerable to high velocity erosion and pitting from heavy metal contamination. To minimize the corrosion in the rich amine, it is recommended that solution loading be kept below 0.34 mole of acid gas (H2S + CO2) per mole of amine. Sidestream filtration is also very beneficial from a corrosion point of view. 5.10.2 Materials Selection 1. Absorber a. b. Shell - CS, 1/4 inch CA, PWHT. Trays - 410S or austenitic SS.
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2.
Lean Amine Cooler a. b. Shell side (cooling water) - CS, 1/4 inch CA. Tube side - CS, 1/4 inch CA (except tubes), PWHT.
3.
Lean - Rich Amine Heat Exchanger a. b. Shell side (lean amine) - CS, 1/4 inch CA, PWHT. Tube side (rich amine). (1) (2) (3) Tubes below 200F - CS. Tubes above 200F - austenitic SS. Tubesheet, channel, and cover - CS, 1/4 inch CA, PWHT.
4.
Regenerator (Stripper) a. b. Shell - CS, 1/4 inch CA, PWHT. Alternate material 410S clad CS. Trays - austenitic SS.
5.
Overhead Condenser a. b. Shell side (cooling water) - CS, 1/4 inch CA. Tube side. (1) (2) Tubes - duplex SS. Tubesheet, channel, and cover - CS, 1/4 inch CA, PWHT.
6. 7. 8. 9.
Reflux accumulator - CS, 1/8 inch CA, gunite lined, PWHT. Reboiler (steam in shell side). Tubes - 410S (12Cr) or austenitic SS. Reclaimer (steam in shell side). Tubes - austenitic SS. Lean Amine Pump a. b. Casing - CS, 1/4 inch CA, PWHT. Trim - 316 SS, 12Cr or Ni-Resist.
10. Piping a. b. All lines containing rich or lean (not fresh) amine solutions shall be PWHT. Lean Amine (1) Below 200F - CS, 1/8 inch CA, 13% Cr valve trim. Above 200F - CS, 3/16 inch CA, 316 SS valve trim.
(2)
c.
Rich Amine (1) (2) Below 200F - CS, 3/16 inch CA, 13% Cr valve trim. Above 200F - CS, 3/16 inch CA, 316 SS valve trim.
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5.11
Sulfur Recovery Units All of the major equipment on claus units, thermal reactors, waste heat boilers, condensers, and catalytic reactors is carbon steel. Hotter vessels, such as waste heat boiler inlets and thermal reactors, are refractory lined. Hot lines are either refractory lined or of austenitic stainless steel. Vapor reheat lines on the latest units have been 310 SS (25Cr-20Ni). Some intergranular cracking problems due to polythionic acid have occurred in vapor reheat lines that are exposed to temperatures above 850F. There have been problems with the tubesheet tube joints in waste heat boilers and refractory and vessel burnouts in thermal reactors. There have been problems with thermal reactor temperature measurement. Some plants have experienced burner problems when complex burner arrangements have been used. Simple austenitic stainless steel, open pipe arrangements have given at least 5 years of service.
5.12
Tail Gas Treating Units Texaco has multi-year experience of treating SRU tail gas by hydrogen rich reducing gas. All of the major equipment of this part of the TGTU, namely feed heater, catalytic reactor, waste heat boiler, quench tower, booster blower, and knockout drum are carbon steel. Feed heater and catalytic reactor are refractory lined. Piping for sour water service is carbon steel with 0.25 inch corrosion allowance. No corrosion problems at this unit have been reported so far. The cooled gas with most sulfur reduced to H2S goes to absorber of MDEA sour gas treating process. Recommendations of the materials for this part of the unit are given in Section 5.10.
5.13
References 1. Corrosion in Petroleum Refining and Petrochemical Operations, J.Gudzeit, R.D. Merrick, L.R. Scharfstein, ASM Metals Handbook, Ninth Edition, Volume 13, Corrosion, 1987. Materials Selection for Refineries and Associated Facilities, R.A. White, E.F. Ehmke, NACE, 1991. Corrosion in the Oil Refining Industry, NACE Conference, Houston, September 1996.
2. 3.
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TABLE 1 NOMINAL CHEMICAL COMPOSITION OF COMMONLY USED ALLOYS (WT %)

MATERIAL Carbon Steel Low Alloy Carbon-0.5Mo 1.25Cr-0.5Mo 2.25Cr-1Mo 5Cr-0.5Mo 9Cr-1Mo AISI 4140 AISI 4340 2.5 Nickel 3.5 Nickel Chromium Stainless Steels Type 405 Type 410S Type 410 Type 430 CA-15 Casting CA-6NM Casting E-Brite XM-27 Cr-Ni Type Type Type Type Type Type Type Type Austenitic SS 304 304L 316 316L 321 347 317 317L Fe Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base Base 36 46 30 8 3 5 5 2

Cr

Ni

Mo
Cu

Zn

OTHER

1.25 2.25 5 9 1 1

2 2.5 3.5

0.5 0.5 1 0.5 1 0.25 0.25

0.4C 0.4C

13 13 13 17 13 13 26 18 18 17 17 18 18 19 19 18.5 22 25 26 21 21 21 22 16 22
0.3Al 0.08C Max

1.0 Max 4
1 1

0.15C Max 0.06C Max 0.1Cb; 0.01N; 0.01C Max 0.08C 0.03C 0.08C 0.03C 0.5Ti 0.8Cb 0.08C 0.03C 0.03C 0.03C 0.03C 0.04C Max Max Max Max Max Max Max Max; 0.14N Max; 0.3N Max; 3.0Cu
10 10 12 12 10 10 13 13 4.7 5.5 7 5.5 24.5 35 33 42 76 62 Base Base 68

2.5 2.5

3.5 3.5 2.7 3 4 2.0 6.5 2.5
Cr-Ni Ferritic-Austenitic SS 3RE60 2205 2507 CD-4MCu (Casting) High Nickel Alloys Alloy Al-6XN Alloy 20Cb-3 Incoloy 800 Incoloy 825 Inconel 600 Inconel 625 Hastelloy B Hastelloy C 276 Monel Copper Alloys Admiralty Aluminum Brass Naval Brass Copper Nickel 90/10 Copper Nickel 70/30 Aluminum Bronze Aluminum Alloys Alloy 3003 Alclad 3003 Titanium Titanium Alloy Corrosion/Heat Resistant Cast Iron Ni-Resist Hardfacing Alloys Stellite 1 6 Tapco 200X 275
3.5
15.5

9 30 16

0.03C Max; 0.21N 1.0Cb; 0.07C Max 0.10C Max 1.0Ti; 0.05C Max 0.15C Max 4.0Cb; 0.1C Max 0.05C Max 4.0W; 2.5Co; 0.01C Max
30 70 77 60 89 69 91
29 21 39

1.0Sn 2.0Al 1.0Sn

1 1 2
10 30
7.0Al
Al Base, Si(0.6), Fe(0.7), Mn(1.5), Co(0.2) Clad with 7072 Alloy: Al Base, Zn (1.3), Si+Fe(0.7) Unalloyed Ti Ti Base, Mo(0.3), Ni(0.8) Base 1-5.5 18-37

2.3-3.0C
C(2.5), Cr(30), W(12), Co(55) C(1), Cr(29), W(4), Co(66) C(4), Fe Base, Cr-Mo Carbides High C, Co Base, Cr-W Carbides
DEC 97
GEMS G-G-1
TABLE 2 ASTM DESIGNATIONS OF COMMONLY USED ALLOYS

MATERIAL Carbon Steel Low Alloy Carbon - 0.5Mo 1.25Cr-0.5Mo 2.25Cr-1Mo 5Cr-0.5Mo 9Cr-1Mo 2.5 Nickel 3.5 Nickel PLATE A285 A515 A516 A204; A302B A387 GR11 A387 GR22 A387 GR5 A387 GR9 A203 GRB A203 GRE EXCHANGER TUBES A179 A214
PIPES A53 A106
CASTING A216

FORGINGS A105 A181 A266
A209 A199 A199 A199 A199 A334 A334 A268
T11; A213 T11 T22; A213 T22 T5; A213 T5 T9; A213 T9 GR7 GR3
A335 A200 A200 A200 A200 A333 A333

P1; A161 T1 T11; A335 P11 T22; A335 P22 T5; A335 P5 T9; A335 P9 GR7 GR3
A217 A217 A217 A217 A217 A352 A352

WC1 WC6 WC9 C5 C12 LC2 LC3
A182 A182 A182 A182 A182

F1 F11 F22 F5 F99
Chromium Stainless Steels Type 405 A240 Type 410S A240 Type 410 A240 Type 430 CA6NM E-Brite XM-27 A176 Cr-Ni Type Type Type Type Type Type Type Type Austenitic SS 304 304L 316 316L 317 317L 321 347 A240 A240 A240 A240 A240 A240 A240 A240
A268 A268
A351 CA15
A182 F430

A351 CA6NM
A268 A213; A213; A213; A213; A213; A213; A213; A213; A789 A789 A789
A731 A249; A249 A249; A249 A249 A249 A249; A249; A271 A271 A312 A312 A312 A312 A312 A312 A312 A312 A790 A790 A790
A351 A351 A351 A351 A351

CF8 CF3 CF8M CF3M CG8M
A271 A271
A351 CF8C

A182 A182 A182 A182 A182 A182 A182 A182
F304 F304L F316 F316L F317 F317L F321 F347
Cr-Ni Ferritic-Austenitic SS 3RE60 (S31500) 2205 (S31803) A240 2507 (S32750) CD-4MCu High Nickel Alloys Alloy Al-6XN Alloy 20Cb-3 Incoloy 800 Incoloy 825 Inconel 600 Inconel 625 Hastelloy B Hastelloy C276 Monel Copper Alloys Admiralty Al Brass Copper Nickel 90/10 70/30 Naval Brass Al Bronze Aluminum Alloys Alloy 3003 Alclad 3003 Titanium Titanium Alloy Corrosion/Heat Resistant Cast Iron Ni-Resist B688 N08367 B463 B409 B424 B168 B443 B333 B575 (N10276) B127

A182 F51 A182 F53

A890

B690 N08367 B468 B163 (Ni-Fe-Cr) B163 (Ni-Fe-Cr-Mo-Cu) B163 (Ni-Cr-Fe) B444
B690 N08367 B464 B407 B423 B167 B444
A296 CN7M

B462

A351 CY40
B622 B163 (Ni-Cu) B111 C44300 B111 C68700 B111 C70600 B111 C71500 C71640

B622 B165

A494 N12M A494 CW12M A296 M35

B171 C70600 B171 C71500 B171 C46500 B169 B209 B209 B265 GR 1,2,3,7 B265 GR12
B467 B467

B148 AL955

B234 B234 B338 GR 1,2,3,7 B338 GR12
B337 GR 1,2,3,7 B337 GR12
B381 B381
A439
DEC 97
GEMS G-G-1
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GEMS G-G-1
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GEMS G-G-1
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GEMS G-G-1
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DEC 97
GEMS G-G-1

Texaco GEMS G G 1 Material Selection Guide For Refinery Process Unit

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DEC 97

MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

4.7 4.8 4.9 4.10

MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

PAGE 2 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT

MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

COMMONLY USED ALLOYS Nominal Composition See Table 1.

ASTM Designations See Table 2.

PAGE 3 OF 85 TEXACO GENERAL ENGINEERING DEPARTMENT

MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

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Cannot be used for long periods at temperatures above approximately 570F.

Problems: Usually costs more than ordinary austenitics and sensitizes.

Problems: Increased cost over austenitics.

Problems a. b. c. Cost. Availability Poor sulfidation, resistance above 1000F.

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MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

Problems a. b. Cost. Availability.

Problems a. b. Cost. Availability.

Problems a. Poor strength over 400F.

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Titanium has very good low temperature strength.

Problems a. Increased cost.

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Problems a. b. Low notch toughness. Poor weldability.

MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS

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Oxid. + ne Oxid.ne (e.g., 2H+ + 2e H2 - hydrogen reduction

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MATERIAL SELECTION GUIDE FOR REFINERY PROCESS UNITS