Mee, BRC-CORP 37.74.F 29 Section 43._VANADIUM PENTOXIDE CORROSION Definition of the Problem Vanadium pentoxide corrosion is the rapid corrosion (fluxing) of a metal surface which occurs in steam boilers and process heaters when fuel containing vanadium pentoxide and/or sodium compounds, is deposited on metal surfaces, Most metals are rapidly corroded by vanadium-containing fuel ash deposits in the temperature range of 590°-815°C (1094-1500°F). Discussion of the Problem Crnde afte Fram contain relatively high concentratione of vanadium and other metals, which are concentrated into the heavy residual fuels during the refining process. In addition, spent caustic and entrained calt in the crude are concentrated in these heavy fuels, In a high temperature environment, metals are inherently stable However, the rate of corrosion is usually limited by the protective action of relatively dmpervious oxide layers. However, when ash compounds of sodium and vanadium pentoxide are deposited on the metal, they can be present as a liquid at certain temperatures (melting point varies with salt composition). The: Liquide rapidly dnerease the corrooion rate, by ectiug flux uf the procective oxide scale, and by transporting oxygen to the metal surface. Because oxygen, which is essential to the corrosion reaction, and is generally readily available, and because V20< is not consumed, the corrosion reaction 4e celf cuctaining ‘80 long as the elevated temperature prevails It should be noted that vanadium as an alloying element in metals can also cause accelerated corrosion because V20s will form as a corrosion Product on the metal surfaces, Lead and molybdenum can act in a similar manner. Combustion of fuels containing significant amounts of vanadium and other metallic salts results in formation of low melting point vanadium pentoxide (ae), vanadates euch a© Nat0-6V:09, o alkali oulfates, which exe wviivolve to metals at combustion temperatures. At very high combustion temperatures, above 1540°C (2600°F), and especially when little excess 0, is present, the sub-oxides of vanadium V203 or VOs are formed. These da not eanse carrnetan Lower temperatures, below 1315°C (2400°F), are most prevalent during coubustion of vanadiun-containing fuels in process heaters and ges turbines. The sodium vanadates (e.g., Na20-6V20s) are the lowest melting compounds and are the most corrosive to metals. These compounds are thought to form by either the vapor phase reaction of NaCl and V20s or by the combination of fine droplets of these materiale upon refractory and uctallic wurfuces in COmDUSTION equipment. Sodium vanadates are most corrosive ovar tha ramperature range of 590-815°C (1100-1500°F). At temperatures below 590°C (1094°F), little or no liquid phase is formed, and the corrosion rates of metals are low. At temperatures above 815°C (1500°F), the maximm corrosion rate shifts towards melts having high proportions of V20s.230 BRC-CORP 37-74.F Excess sodium hydroxide in the fuel can also be troublesome, as the alkali reacts with the S03 present in the gas strean to form a range of alkali sulfates, which in themselves are highly corrosive to metallic components. In addition, the combination of alkali sulfate plus V20s can result in compound having melting points as low as 315°C (600°F). This situation is only encountered vhen alkali is present in anounts in excess of that which can react completely with ¥205, vince the formation of alkali Vanadates is favored over that of alkali sulfates. Table 43-1 liste tolerance levele for vanediuu du fuels, for furnace tubes and furnace tube hangers of 25Cr/20Ni. Tal LEVELS FOR VANADTIM TH FUELS Vanadium Maximum Concentration ‘Temperature Comments > 150 ppm 650°C (1200°F) Corrosion of metals intolerable above 650°C (1200°F) 20 to 150 ppm 650 to 845*c Active corrosion, but can be tolerated (1200 ra 1850°R) — deponding on the Na/V ratio, the wetal temperature, and the sulfur content (More data needed to define limits better in this area). < 20 ppm 845°C (1550°F) Corrosion rates should be under 20 mils/yr. <5 ppm 1095°C (2000°F) Corrosion rates should be under 20 atle/yr. Methods of Checking for the Problem The form of attack is unique. (See Figure 43-1). Metal appears to have been washed away in pools. High vanadium contents are found in the corrosion Product. Sodium 1s usually present, Methods of Eliminating the Problem Uae of low vanadium and sodium content fucle is the best appiuach to controlling the problem. Washing fuels before burning to remove sodium and adding inhibitors to minimize the effects of Vz0s, are possible additional steps for control. Washing the of] with water solutions can reduce the sodium im the fuel ofl but will not reduce the vanadium content. If practical, reducing the temperature of operation below that at which molten vanadium salts form [about 625°C (1100°F)] is an effective means of eliminating the problen. High chromium alloys offer the best fuel ash corrosion resistance Field experience hae shown the $0Cr/S0N1 aud GOCL/40NL alloys have been SUC~ cessfully used, However, since most components still suffer high corrosion Fates when in contact with vanadium-sodium fuel ash melts, they should be designed to minimize the amount of surface araa ava(lablo on which ach may accumulate, deccccccceccccect Acccccccveccccvesd .t 6° é Coe coe ccccecseces 7 remem mela OA BRC-CORP 37:74.F 231 Monolithic refractory coatings and metallic coatings have been applied to metal components in furnaces to provide protection against aggressive fuel ash deposite, O41 additives, introduced as suspensions of metallic oxides or their alts (e.g. Mg(OH)2, Ca(OH) or Al20s), have been used for several years to keduve the severity of attack trom V2Us compounds. The purpose of the additive is to form high melting point compounds with vanadium which, if not molten in the fuel ash deposit, do not cause rapid corrosion. Limiting excess air levels to 1-5% also reduces fuel ash corrosion by inhibiting the formation of SO; and Vz0s in the combustion products while favoring the formation of less troublesome lower oxides (S02, V20,, and Vz03). The power industry has had some success with this method in steam boiler: Pitfalls ‘Among the difficulties encountered when trying to limit corrosion from vanadium or sodium containing fuel ash deposits, are the following: GQ) The alloys with the best resistance, 50Cr/SON1 and 60Cr/40NL types, have traditionally had poorer stress rupture strengths than their ferrous based alternatives. They are also more expensive, less available, and have generally poorer sulfidation resistance. (2) Experience with refractory coatings to protect metallic hardware iu furnaces has been generally less than satisfactory, due to large thermal expansion mismatches between the metal and refractory. Failure usually occurs upon thermal cycling, which causes cracking, eventual spalling of the refractory, and direct expeoure of the metal to the effects of the fuel ash. (3) Use of of1 additives for inhibition of fuel ash corrosion has been generally shown to be uneconomic, sometimes ineffective, and to cause increased tube fouling problems. (4) Use of low excess air levels to retard formation of the corrortva 20s, presents probiems in practice due to the need for precise furnace burner controls, extra operator attention, and pollution control. (5) Water waohing the fuel vil cuald bring about a Na/V ratio that would cause more severe corrosion than the deposits from unwashed fuels, It is generally believed that deposits in the vicinity of a Na/V ratio of 0.2 are the most corrosive.e ne BRCCORP 37-745 -e e @e 8 Figure 43-1 View of Steel Pipe After Attack by Vanadium Pentoxide Peeocee e0eceooee