Age eee cece es BRC-CORP 37.74.F 129 Section 26. HYDROGEN CHLORIDE CORROSION Definition of che Tivview Hydrogen chloride corrosion is an example of severe general corrosion by a strong mineral arid, HCl te found in refinery upesativae as a Cone faminant of ofl streans and in acid-gas condensates. It is also prevalent in many chemical processes, such as: n-olefins for detergent alcohols; ally) chloride, ethyl chloride, and VOM manufacture; catalyst hydrolysis in poly- Propylene plants; vapor phase corrosion in chlorinated hydrocarbon storage tanks; and incinerators during start-up and shut-down. Matesials of construction to resist the corrosiveness of hydrochloric acids of varying strength are fairly well established (see Figure 26-1). However, hydrogen chloride corrosion yields its vorst problens when a liquid Phase (mainly water or polar organics) ueayectedly condenses out of a gle Stream with the initial droplets being highly concentrated acid (see Section 11 on Condensate Corrosion). At temperatures, less than approximately 30°C (about 50°F) above the dew point. rapid corrosian of many metalo, particularly steiiless Steels, occurs, While 1iquid phase (dew point) corrosion is prevalent at lower temperatures, HCl gas/metal reactions become more prominent at temperatures above about 250°C (about 480°F). This situation prevails in equipment euch as incinerators for chemical wastes, Discussion of the Problem Crude of1 contains up to 0.04% colt. MgClz eud Cacl2, amounring to roughly 15% of the total salt, can be hydrolyzed and can release HCl upon contact with steam. To minimize the problem, desalting facilities are installed, and aqueous caustic solutions are injected into the crude of] stream for conversion of these salts into less troublesome NaCl. However, the reaction 1s Rot complete and the addition is further limited because of the danger of caustic embrittlement of furnace tubes and transfer lines, particularly 60 when sweet crudes are processed. Therefore, some HCl always remains, which then corrodes downstream overhead equipment when HC1 and Hz0 components in the system are cooled below their dew point. However, before condensation occurs, HCl is neutralized with amonia in such a way that a pH between 6 and 7 is obtained in the accumulator. Under these conditions, carbon steel surfaces are pratacted by an dren oulfide fila, Gareful neutralizing procedures must be followed because, at too low a pli, the iron sulfide film becomes soluble, while, at too high a pl larger amounts of chloride ions apparently weaken the protective film. Generally, the higher the H2S partial pressure (sour crudes), the lower the pH at which a protective iron sulfide film is formed (more H¢1 tolerable) and at which inhibitors are active. Inhibitors for this service are fatty amines, amides from fatty acids and amines, or derivatives of cyclic organic amines,130 BRC-CORP 37-74.F If large amounts of HCl are neutralized, ammonium chloride may condense out and cause fouling and corrosion problems of its own. For these vases, @ water yuench has Deen recommended, Sufficient accumulator water must be recirculated to move the dew point of undesirable stream components to the injection point and dissolve and dilute then adequately. In catalytic reformer regeneration trains, corrosion 1s most severe at the time of HCl breakthrough after the catalyst re-chloriding operation. Good temperature control of the air cooler carbon steel tubes is vital. If their skin temperature is not at least 30°C (about 50°F) above the HC1/iiz0 dew Point of the process gas stream, then the dew point has to be lovered by lowering the steam and HCl concentrations in the systen. In butane isomerization, a solution of aluminum chloride in antimony chloride promoted by anhydrous hydrogen chloride is used as a catalyst. Portions of the plant dn contact with the liquid catalyst at the operating temperature of 60° to 100°C (140 to 212°P) require high-nickel alloys. Isomerization catalyst sludge can be regenerated with hydrogen at 1000 pei and 175°C to 205°C (347 to 401°F) using nickel or Inconel equipment. Hastelloy R ta sme: factory, being subject to intergranular attack, which is worsened 1f the alloy is sensitized. The addition of 0.1% powdered aluminum to the molten salt reduces the corrosion of Inconel and nickel from about 50 mpy, minimm, to Jess than 20 mpy, maximum. Aluminum addition does not benefit Hastelloy B. With aluminum inhibition, temperatures at the high end of the range are unsatis- factory. Almost any construction material is suitable for dry hydrogen chloride gases at room temperature. However, as can be seen from the following table, the uppar tamparatura limit far continuous service for matale im pure hydrogen chloride varies significantly. Additionally, the HCl content of combustion gases at high temperature is thought to affect the oxidation resistance of boiler and incinerator materials of construction, though the exact effect is not yet well defined. Table 26-1 ~ MAXIMUM SUGGESTED TEMPERATURE FOR ‘GONTINUOUS SERVICE IN URY HIDROGEN UMLUKIUE Hydrogen Material Chloride, *c (°F) Platinum 1204 (2200) Gold 811 (1600) Nickel 510 (950) Inconel 482 ( 900) Hastelloy B 454 € 850) Hastelloy C 454 ( 850) Carbon steel 250 ( 480) Monet 252 ( 450) Silver 232 ( 450) Cast iron 204 ¢ 400) 18-8 Mo 499 ¢ 750) Copper 93 ( 200) * Pocccccccccccccce eoen0e7°"? é Ae eee a. BRC-CORP 37.74.F 131 Methods of Checking for the Problem Corrosion by aqueous hydrogen chloride is a severe form of corrosion which is usually quite obvious and does not require any detailed examination, beyond visual inspection. Sometimes external nondestructive examination methods will reveal a reduced wall thickness due to HCl corrosion. Clogging of Lines with corrosion product sometimes indicates the advanced stage of attack. Methodo of Eliminating the Problem As discussed in the preceeding sections, a variety of measures can he taken to minimize attack by mofat HCI. General methnde tnetnde+ (1) Selecting more resistant materials of construction if liquid phases are present and condensation cannot be prevented. (2) Controlling humidity to lover the dew point of the system, so that the equipment stays at least 30°C (about 50°F) above the dew point. (3) Neutralizing the acid before or during condensation. (4) Adding inhibitors and creating flow patterns eo that the aqueous phase {s not in contact with the tube wall. (9), Giving a caustic wash to equfpment which during shut-down has passed through the HCl/solvent dew point temperature range. Pitfalls When evaluating the possibility of HC1/H20 dew point corrosion, the metal skin temperature has to be taken into account, and not the process stream temperature. A rise in metal skin teuperature has to be sufficiently great to move the dew point 30°C (about 50°F) above the HC1/H20 dew point. A temperature rise which still leaves the metal skin temperature below the dew point only inereases corrasion. Al] susceptible areas hava to be kept 30°C (about 50°F) above the HCI/H20 dew point; otherwise, dew point corrosion will simply be shifted to other locations. When selecting materials of construction to resist HCl corrosion, careful consideration must be given to impurities in the process stream that could cause rapid corrosion of metals normally resistant to hydrochloric acid environments (e.g. contamination witn nighly oxidizing species).Temserature, "F BRC-CORP 37-74.F 28 @$p RA Bolling Point 160 120 o 10 20 30 40 Concentration, HCI, Figure 26-1 Corrosion Resistance of Materials to Hydrochloric Acid Corrosion Rate lest then 0.020 inches per year eo ébetetadady Ty edad ad dada ah Medal de] BRC-CORP 37-74. Figure 26-1 (Cond) 133 Code for Hydrochlorie Acid Chart Materials in numbered zones having reported corrosion rate less than 0.020" per year. Zone 1 Chiorimet 2 Glass Platinum ‘Tantalum Hastelloy 8 Durichlor (FeCl Free) Saran Rubber Silicon Bronze (Ait Free) Copper (Air Free) Nickel (Air Free) Monet (Air Free) Zirconium Tungsten Titanium ~ Up to 10% HCI at Room Temp. Worthite ~ Up to 2% HCI #t Ravi Tens Zone 2 Chlorimer 2 Silver Platinum Tantalum Silicon Bronze (Air Free) Zirconium Molybdenum Impervious Graphite Zone 3 Chiorimet 2 Glass Platinum Tantalum Hastelloy B (Chlorine Free) Durichlor (FeCly Free) Havea Saran Rubber Motybdenusn Zirconium Impervious Graphite Zone 4 Chiorimet 2 Giass Silver Platinum Tantalum Hasteloy B (Chlorine Free} Durichlor (FeCl Free) ‘Monel (Air Free ~ Up to 0.6% HCI) Zirconium Impervious Crephite Tungsten Zone 5 Chlorimet 2 Glass Haveg Silver Platinum Tontalum Hastelloy B (Chlorine Free) Zirconium Imoervious sohita