Cece, eco ee eeeeeeee Ss BRC.CORP 37.74-F _ Section 28. HYDROGEN SULFIDE CORROSION Definition of che Problem Hydrogen sulfide (H2S) which causes corrosion by metal loss is discussed in this section. Hydrogen eulfide alec causco other forms of damage, €.g., blistering, eubrittlenent, and sulfide stress cracking; these aspects are covered in other sections of this report: [see Hydrogen Blistering (Section 25), Hydrogen Enbrittlement, (Section 27), Hydrogen Attack (Section 24) and Stress Corrosion Cracking (Section 37)], Environments which produce metal loss by hydrogen sulfide attack considered in this section are 1) aqueous hydrogen sulfide solutions, 2) sulfur bearing oils, and 3) hydrogen sulfide plus hydrogen environments. Discussion of the Problem Corrosion in Aqueous H2$ Solutions Aqueous H»S corrosion is 2 common problem in the separation and Processing of oil from distillation through catalytic cracking, coking, de- sulfurization, and hydrocracking. Trouble areas are usually in condensers, exchangers, and accumulators dovnstream of H2S producing units. Aqueous hydrogen sulfide corrosion is seldom a problem in chemical plants except those Processing hydrogen feed stocks, as in condensing areas of plants producing olefins by thermal cracking. Solutions containing only hydrogen sulfide and water cau Le yulte corrosive to steel, However, very high initial rates of attack decrease rapidly with time, unless erosive conditions remove the protective sulfide scale. Both general attack and pitting occur. In of1 and chemical processes, hydrogen sulfide is seldom encountered without other compounds, usually ammonia and often hydrogen chloride, which materially change the corrosion behavior of the ayatem. ‘The presence of ammonia, as in hydrotreater effluent, raises the pl of the solution and Feduces the corrosiveness, as compared to the H2S-H20 system, until the con~ centrated alkaline NH,HS regime is reached. Severe corrosion by alkaline NMS nas occurred in the latter passes of catalytic cracker hydrotreater air coolers, In addition, corrosion by NH,HS has occurred in sour water stripper systems. The presence of HCL, as in crude column overhead streams, tends to Promote pitting, which ie aggravated by sulfiding conditions. Corrosion in Sylfur-Bearing 041 In the absence of liquid water, of1 streams containing organic sulfides are appreciably corrosive to carbon steel only when hot. The corrosive is H2S evolved at high temperature. High temperature sulfiding attack is commonly found in ofl separation and cracking processes, e.g. crude distillation (atmospheric and vacuum) furnaces and colums, and in thermal and catalytic crackers. Sulfiding occurs also in handling Products of hydroprocessing units, which is discussed in the next subsection on corrosion by high temperature H2S plus Hz.142 BRCCORP 37-74.F The most important characteristic of a eulfur-containing ofl is the ease with which sulfur compounds thermally decompose to produce W2S. A number of teste have been devised to measure this corrusiveness. The auvuut of 425 evolved 1s a mich more reliable indicator of corrosiveness than total sulfur content, since the oil may contain stable, inert sulfur compounds, that normally contribute little to the corrosion potential. Corrosion in High Temperature H»S Plus Hp Environments Corrosion by hydrogen sulfide in the presence of hydrogen occurs in the same temperature range as corrosion in sulfur bearing oils without hydrogen. However, there are some important differences; hydrogen may, and often does, increase the corrosiveness of the system, But on occasion. hydrogen may pre vent corrosion, e.g. where the H2S/Hz ratio is low (below the equilibrium line, see Figures 28-1, 28-2 and 28-3) enough to insure that the metal, rather than ite sulfide, is the thermodynamically stable form. In most cases, hydrogen increases sulfiding severity of ofl systems One factor is the reduction in tendency to form coke deposits in the presence of hydrogen. Lack of coke dn the oulfide ocales reduces thelr protective qualities. There are also other factors which contribute to increased corrosive attack in the presence of hydrogen, but which are not well understood. Methods of Checking for the Problem The most generally applicable method of detecting HzS corrosion is by wali thickness measurement. This can be done, often during operation, by ultra- sonic measurements or by radiography. During down time, visual observations can be made, or direct wall thickness measurements obtained. For small tubes, Anoide diauele: weasuieuents can be obtained from calipers or a number of types of gauges operating on mechanical or magnetic principles. Corrosion in aqueous HaS systems can sometimes be detected by appearance of black iron sulfides in water samples. Methods of Eliminating the Problem Aqueous Hydrogen Sulfide Usually carbon steel is resistant enough to be the economic choice for aqueous sulfiding conditions. Under severe conditions, such as crude colum overhead condensers and hydrotreater air coolers, supplementary measures are often required to control corrosion of carbon steel. These include pH sontrol by ammonia, addition of filuing aulue cype corrosion inhibitors, and Water injection. Stainless steels provide good corrosion resistance in critical areas, such as valves, : ° e e e e e e e . e 20 ° Sulfur Bearing Oils A temperature of 260°C (500°F) is often used as an approximate economic upper Limit for the use of carbon steel. This temperature should be used only as a guidepost, since the actual economic limit for a specific system may differ considerably, depending on both the characteristics of the ofl and requireweats of cle eyulyment. PrcccccccccccccesSOOO CHOCOOCHOCOE Oe ee eee BRC.CORP 37-74.F 143 Chromium steels and, under very severe conditions, chromiun-nickel steels, are preferred for resistance to high temperature sulfiding. A number of correlations of corrosion rates vo. temperature for common otructural alloys have been proposed. The curves from the data compiled by the API Subcommittee on Corrosion provide a broad background of experience in desulfurizers in the absence of hydroren. A set of guidelines developed from this survey is presented in Figure 28-7. High Temperature H2S Plus He Attack by high temperature HzS gas produces sulfide scales that can range from silver to black, depending on such things as the stage of development, and the amount of coke contamination, sulfide corrosion products on ferrous alloys start as fine grained scales, but the outer layer develops into a coarse columar form (see Figure 28-4). Scales on carbon and low alloy steels’ (con— taining 1-2%Cr) are not very adherent and tend to spall as they grow thicker. Chromium steels and chronium-nickel steels produce tighter, finer grained sulfide scales, which can be very tenacious, especially on the inside of pipes where they are under compression, Formation of these tenacious scales shields the alloy from attack and retards corrosion. Metal loss is generally uniform, but pitting and localized area attack can occur, particularly in areas of severe flow conditions. Figures 28-5 and 28-6 are examples of furnace tube pitting trom H2S. A chromium content of 9% in steel is effective in reducing sulfiding attack under hydrosulfurizing conditions [350°-400°C (662°-7752°F) and 10-50 psia H2S; see Figure 28-1], but 12% or more chromium is often required under higher temperature reforming conditions. The choice of resistant alloys e.g. 12% Cr, 17% Cr steels or higher Fe-Cr-Ni alloys, normally in bared on factors other than sulfiding corrosion resistance. These factors include Susceptibility to stress corrosion cracking and to microstructural changes which decrease their usefulness, e.g. 885°F embrittlement, (see Section 15) sensitization (See Section 29), and signa-phase formation’ (See Section 35), as well as practical considerations such’ as mechanical properties, cost, availability and ease of fabrication. Figures 28-1, 28-2 and 28-3 show data for ferrous alluy» obtained from desulfurizers and catalytic reformers. Some recent cata from specimens exposed in hydrocrackers for several years show corrosion rates appreciably lower than indicated by these curves, 60 that these curves serve as a conservative guide. Pirfall ‘The curves for corrosion in hot, sulfur bearing oil systems (Figure 28-7) and for H2S-Ha systems (Figures 28-1, 28-2 and 28-3), should be used primarily as guidelines to provide approximate or relative corrosion rates; actual corrosion rates are dependent on many variables. ¥rimaty variables tor a given alloy normally include composition of the stream, flow conditions at the metal surface, and the metal temperature. In addition to these primary variables, there are many pertinent eccondary variables te concider. Tor example, stream composition not only includes consideration of sulfur content, but also the form in which the sulfur exists, i.e., the extent and rate at which the sulfur compounds decompose to HaS. Other factors in stream compositional BRC-CORP 37-74.F which can be important include the water and the salt content of the stream. Flow conditions not only include velocity, but may include phase conditions and turbulence factors. Metal temperatures may he as mich a= S6-111°C (100-200°F) higher than stream temperature if a furnace is pushed to capacity and the tube surfaces become fouled. Ideally these factors should be known in detail before alloy selection is made. In practice, this information is slmvet uever available, in which case corrosion engineers knowledgeable in the field should be consulted. In contrast to hot sulfur bearing ofl systems, H2S plus Hz environments require a minimum of 9-12% chromium to appreciably improve corrosion resistance over that of carbon steel. Small percentages of chromium are of no significant benefit in the HaS plus H2 environnenta. Use of 18Cr-8Ni or other austenitic stainless steels to resist HS corrosion must also be based on an assessment of their susceptibility. in the system under consideration, i.e., to chloride stress corrosion or poly- thiondc acid attack (see Section 37 on Stress Corrosion Cracking). & PocccccneccccccceSZ.c voceccccccccocegcoce reer eeerre* BRC-CORP 37-74.F 100 id Pressure, psi oor} 0.001 315 370 600 700 Based on Long Term Refinery Data lsocorrosion Curves are for 0-5 Cr Steels (rils/year) Citcied Numbers Indicate Corrosion Rate for 9 Cr Stee! (mils/vear) Fee § Equilibrium Line for 600 pi H omer {irom Trermedynamie Date) 4 480 535 590 easrc 800 800 1000 1100 1200°F Temperature Figure 28-1 Under Hydrorafining Conditions for 9% Cr Steet up to 5% Chromium 145146 HS Partial Presure, psi BRC-CORP 37-74. ‘Shapes of Curves Predicted from Laboratory Studies Fe-Fe § Equilibrium Line for S600 psi He (from Thermodynamic Data) wut 0001 CL... 315 a0 425 480 535 500 eastc 0 700 800 900 1000 1100 1200°F ‘Temperature Figure 28.2 ‘Sulfiding Corrosion Rates for 18 Cr8 Ni Stee! (Type 304) Under Hydrorefining Conditions Povccccccccccccceeee ee oe: e e BRC-CORP 37-74-F 100 Shanse of Cues Breicted from Laboratory Studies HS Partial Pressure, psi Fe-Fe § Equilibrium Line for (600 psi H (from Thermodynamic Data) ogy LP tt 318 370 425 480 535 500 asic 600 700 800 900 1000 1100 1200°F Temperature Figure 28-3 Sulfiding Corrosion Rates for 12 Cr (Type 405) Under Hydrorefining Conditions 147148 Sulf Figure 28-4 Scale on 12 Cr Stool Magnification: 100X. BRC-CORP 37-74.F Outer Seale Inner Scale Steel * PoccccccccccescesBRC-CORP 37-74. 149 Figure 28-5 Mur Containing Crude Oi! Furneve Tube Fitting z $ g 8 ey x e e e e e e e e e e e Figure 28-6 ‘Spiral Pitting Pattern on Carbon Steel Outlet Tubes ‘Magnification: 4X,150 1009; 100 ou BRC-CORP 37.745 Average Corrosion Rates ‘Average Sulfur: 0,6%w \ Carbon Stee! \ 1-3%6r \ 4- 8% Cr 9% Cr 260 215 370 wesc 500 600 700 00°F Temperature Figure 28.7 High Temperature Sulfiie Corrosion in Hydrogen-Free Environment AOOOCOCCOCOLOOOL COLE: Sccecece cccecoet F