be Co Ce ee eee BRC-CORP 37-74. im Section 32, NAPHTHENIC ACID Definition of the Problem Corrosion of carbon and alloy steele has been observed in crude of] containing naphthenic acids in the temperature range of 220-400°C (428-752°F). The corrosion occurs primarily in crude and vacuum distillation units, but also is found in hydrotreater preheaters. The most severe corrosion occurs in areas of high velocity, impingement, or turbulence. Discussion of t! Problem True naphthenic acids are naphthenic carboxylic acide represented by the formula XCOOH (X represents a cycloparaffin radical). However, the term aphthendc acide de used collectively for all orgeule acids preweut in crude ofl. The molecular weight of naphthenic acids extend over a wide range but most are found in gas ofl and light lubricating oil weight fractions. Corrosion by naphthenic acids is independent of the presence of water. The corrosion products, iron naphthenates, are soluble in the ofl Phase. Therefore, formation of a protective film is prevented. ‘The appearance of naphthenic acid corrosion varies from sharp edged, crater-like pits to sharp edged, streamlined grooves. The surfact xeterally very clean witn no evidence or corrosion products (see Figures 32-1 and 32-2). Severe corrosion has been observed on carbon steel, chromium steels, and Type 304 stainless steel. Type 316 stainless steel, vhich normally hae good reeietance to naphthenic acide because of ite molybdenum content, hae experienced corrosion in conditions of extreme velocity or impingement. are No corrosion occurs above 400°C (752°F); at this temperature naphthenic acids decompose. Naphthenic acids also will decompose at temperatures below 400°C (752°F) in hydrorefining unit reactors. Corrosion attributable to naphthenic acids has not been observed downstream of these reactors. Methods of Checking for the Problem ‘The presence of napnthenic acids an crude 011 can be determined by chemical analysis. The level of naphthenic acids in crude of] ie normally found by titration with potassium hydroxide. Naphthenic acid corrosion is generally considered to be a eignificant problem only when the acid neutralization number exceeds 0.5 mg KOH per gram of ofl. However, a correlation between the severity of corrosion and the magnitude of the neutralization number has not been established conclusively. In fact, sone differences in corrosion experiences of different crudes can not be explained soley on acid neutralization number. A corrosion test using coupons of Types 304 and 316 stainless steel may indicate the presence of the acid. If Type 304 stainless steel is severely corroded but Type 316 is unaffected, there is reason to suspect that naphthenic acids are present in the ofl strean.172 BRC-CORP 37-74.F hods of Eliminating the Problem Naphthenic acids can be removed from ofl fractions by neutralization with caustic. For light fractions, aqueous solutions of NaUH can be used to extract the acids, For heavier fractions such as lubricating oils, it is necessary to neutralize during high vacuum distillation, and to draw off the phehenate salts ac a efde otrean, If neutralization is impractical, control of corrosion can be achieved through use of Type 316 stainless steel. Type 316 is used primarily in this application as a liner or integral cladding only, because of the susceptibility of this alloy to chloride stress corrosion cracking. The curves in Figure 32-3 give an indication of the corrosion resistance to naphthenic acids provided by various materials. Pitfalls When severe corrosion is encountered in crude streams, there is some chance that the problem can be too easily assumed to be the reault of naphthenic acid attack, Attack may well have resulted fron the action of sone ether corrosive medium, Therefore, proper solution requires a careful analysis of information concerning stream composition, pressure, temperature, flow rates, and the alloy. If Type 316 stainless steel is utilized to prevent corrosion from naphthenic acid, consideration mist also be given to the possibility of poly- thionic or chloride stress corrosion cracking (see Section 37). « Poece ©0000 88008BRC-CORP 37-74.F 173 Figure 32.2 it Acid Corrosion of » Carbon Stes! Bend te was caleulated to be 0.66 inches per yeer. Mognification: xX. “The corrosion ooo ©0000 0C8 §.174 BRC-CORP 37-74.F se e e ele . e e e e iat] e@ e e e e 3 e : e 3 / We -e e } e seer sree. e e {We = 13-3 STEEL e pe . { e e e e a e e hers ste rete e ane e ==} < 7@ : Fe 228 . Coren ot Suda Cate Ot Gsin Nap Ald and Sulfur Compounds * e e