MATERIALS OF CONSTRUCTION

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SULFURIC ACID MANUFACTURING

Introduction The following is a description of materials of construction for sulfuric acid manufacturing plants. Emphasis is on potential damage mechanisms and failure modes.

Background Materials of construction in sulfuric acid manufacturing plants are typically limited to carbon steel, refractory-lined carbon steel, Type 304 or 304H stainless steel, and Incoloy 800H. Carbon steel is used in cooler sections of the plant, typically at temperatures below about 900F. Carbon steel may be lined with a polymeric coating for corrosion resistance when operating temperatures are low enough for acid condensation. Refractory-lined or brick-lined carbon steel is used in the hottest sections of the plant, where temperatures typically exceed 1800F. Types 304 and 304H stainless steels are used in ducting that operates in the 900-1200F temperature range.

Section-by-Section Discussion Upstream of the Sulfur Furnace Normal operating temperatures upstream of the sulfur furnace are typically below 275F. In this part of the plant, carbon steel is the material of choice. The sulfur content of the gas stream is very low here, but even the slightest amount of sulfuric acid condensation can cause rapid corrosion of carbon steel. Figure 1 shows corrosion rates for carbon steel in sulfuric acid. The corrosion rate depends on acid concentration and temperature. Corrosion rates are extremely high in weak acid even at ambient temperature. Below 60% acid, the corrosion rate for carbon steel can exceed hundreds of mils per year (mpy). Acid that condenses on carbon steel during shutdowns will aggressively corrode carbon steel. Above 60% acid, corrosion rates are lower due to the formation of a semi-protective sulfide scale. In the 60-98% acid range, the corrosion rate is highly dependent on temperature. Above about 125F, acid concentrations in this range will corrode carbon steel at 50 mpy or greater. Corrosion rate will exceed 200

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mpy in this acid range when the temperature exceeds about 225F. Corrosion rate drops again in a small acid range of about 98-100%. Corrosion of bare carbon steel in this section of the plant may occur during shutdowns if sulfur is present and if moisture condenses on ducting and equipment. Condensing acid will run the full range of acid concentrations. In order to combat corrosion of carbon steel during shutdowns in this section of the plant, bare steel must be kept out of contact of condensing acid. Methods include coating the steel with an acidresistant polymeric coating, purging equipment of sulfur prior to opening the equipment for shutdown, and keeping metal skin temperatures above the dew point during the shutdown. Sulfur Furnace and Waste Heat Boiler Normal operating temperatures in the sulfur furnace, waste heat boiler (WHB), and associated piping exceed 1800-2000F. In this part of the plant, brick-lined and refractory-lined carbon steel is the only economical material of construction. Brick and refractory linings insulate the carbon steel equipment and ducting, and reduce actual metal skin temperatures to below about 900F. Below 900F carbon steel has sufficient mechanical strength and oxidation scaling resistance. When the brick or refractory lining is damaged by cracking and spalling, carbon steel can be exposed to hot furnace gases. In such cases, high-temperature sulfidation and oxidation of the steel occurs behind the brick lining. Refractory and brick must be closely inspected during shutdowns and repaired, if necessary. The inlet ducting to the sulfur furnace is fabricated from Type 304H stainless steel since it can potentially see high temperatures from its proximity to the furnace and from backflow of hot furnace gases. The ASME Code temperature limit for Type 304H plate and piping is 1500F. Above about 1050F, strength drops rapidly and high-temperature creep becomes an issue. Creep must be considered if Type 304H is intended for use between 1050F and 1500F. Strength and corrosion matters specific to 300-series stainless steels are discussed later in the section entitled "Issues Concerning Stainless Steels." Converter and Converter WHB Converters are fabricated from carbon steel, low-alloy chrome-moly steel, or stainless steel depending on the particular design. Gas from the furnace WHB is heated exothermically in the top catalyst bed of the converter. The exit temperature from the top catalyst bed is high enough to preclude the use of carbon steel or chrome-moly steel for the ducting to the converter WHB. Type 304H stainless steel is commonly used here. Process gas leaves the converter WHB at reduced temperatures, is returned to the converter and then travels downstream. Temperatures are once again low enough in this section of the plant to allow the use of carbon steel.

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Issues Concerning Stainless Steels Types 304, 304H and 304L Stainless Steels There is sometimes confusion between the use and properties of Types 304, 304H, and 304L stainless steels. The alloys have generally the same chemical composition, except that Type 304 has a maximum carbon content of 0.08 wt.%, Type 304L has a maximum carbon content of 0.03 wt.%, and Type 304H has a required carbon content of 0.04-0.10 wt.%.

Specific heats of stainless steel can be dual-marked, meaning that a steel containing 0.02 wt.% meets the chemistry specification for both 304 and 304L, and may be stamped "304/304L." Similarly, high-carbon heats can sometimes be stamped "304/304H." The higher carbon content of Type 304H affords it better high-temperature strength, which is needed for the sulfur furnace inlet ducting and for ducting from the top catalyst bed of the converter to the converter WHB. The ASME Code allows the use of Type 304H to 1500F. Type 304 is allowed to 1500F only if it contains at least 0.04 wt.% carbon. Due to the lower carbon content of Type 304L, the Code restricts its use to 1200F. Furthermore, Type 304L is subject to high-temperature creep deformation above about 900F. Type 304L can be used for expansion joint bellows upstream of the sulfur furnace where temperatures are fairly low. In relatively lowtemperature service, Type 304L may be preferred over Types 304 and 304H due to its higher resistance to a damage mechanism known as sensitization, which is described next. Sensitization, Corrosion, and Stress-Corrosion Cracking of Stainless Steels All 300-series stainless steels (including Types 304, 304L, 304H, 321, and 347) are subject to a degradation mechanism known as sensitization. Sensitization is time- and temperature-dependent, and occurs as the result of high-temperature exposure above about 750F. It is especially rapid in Types 304 and 304H stainless steel. Sensitization will occur during the short time it takes to weld Type 304 and 304H components, but can take hundreds or thousands of hours to become significant in Types 304L, 321, and 347. During sensitization, chromium reacts with carbon to produce agglomerated chromium carbides on grain boundaries within the steel. The coarsening of these carbides over time depletes the grain boundaries of chromium. The local depletion of chromium makes the grain boundaries less corrosion-resistant and subjects them to accelerated corrosion in sulfuric acid and to potential stress-corrosion cracking (SCC) in sulfurous acid. While non-sensitized 300-series stainless steels will resist corrosion from acid condensation during shutdowns, sensitized material may not. Table 1 lists the temperature range in which sensitization can occur in common 300-series stainless steels. Types 304 and 304H are the most susceptible. Type 304L is less susceptible than 304 and 304H because of its lower carbon content. Types 321 and 347 are less susceptible because they are stabilized with

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strong carbon-formers. Type 347 is stabilized with niobium and will sensitize only in a very narrow temperature range. It is a good choice for expansion bellows that operate up to about 925F. If sulfur-containing acids condense on sensitized components during shutdowns, corrosion and stresscorrosion cracking (SCC) can occur. As with the corrosion of carbon steel, bare sensitized stainless steels must be kept out of contact of condensing acids during shutdowns. Simple field metallography techniques, such as replication, can help to determine whether stainless steel has been sensitized in service. Stress-corrosion cracking is exacerbated by sensitization, but can occur even in non-sensitized stainless steels. Chloride SCC is the main concern in non-sensitized material. Chlorides are present in rainwater and some insulating materials. Rainwater that wets insulation and reaches bare stainless steel beneath the insulation can carry enough chlorides to cause SCC. Chloride SCC can be avoided by stress relieving stainless steel welds at 1550-1650F for one hour per inch of steel thickness (and 1 hour minimum).

Expansion Joint Bellows Materials Choices for Expansion Joints Bellows Expansion joint bellows are used to reduce thermal expansion stresses in ducting. Depending on the service temperature, bellows can be fabricated from any of the 300-series stainless steels or from Incoloy 800H. Incoloy 800H is an iron-nickel-chromium alloy containing roughly 40 wt.% iron, 30-35 wt.% nickel, 19-23 wt.% chromium, with additions of aluminum, titanium, and carbon for high-temperature strength and creep resistance. The ASME Code temperature limit for Incoloy 800H is 1650F. The increased high-temperature strength and corrosion resistance of Incoloy 800H over Type 304H makes it the material of choice for expansion bellows that operate at 1000-1650F. Below 1000F, Type 304 is acceptable from a strength standpoint, but Type 347 is usually a better choice due to its sensitization resistance. Creep Ductility and Sensitization of Incoloy 800H The alloy chemistry of Incoloy 800H material intended for use in expansion joints is controlled to reduce the risk of long-term embrittlement and creep ductility failures. Reputable expansion joint manufacturers, such as Super Flexonics/Pathway, should be consulted when specifying Incoloy 800H bellows for hightemperature service. Industry experience is that the total limit on aluminum plus titanium content must be controlled to 0.4-0.7 wt.%. Increasing aluminum and titanium content beyond these limits increases the risk of brittle failures due to long-term aging in the 1000-1400F temperature range. For thin-walled bellows, an ASTM grain size of 2-5 is required for creep resistance. Embrittlement and creep ductility losses in Incoloy 800H are associated with the formation of an intermetallic precipitate known as gamma prime, which consists of nickel, aluminum, and titanium (Ni3Al

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and Ni3Ti). Gamma prime forms after long-term exposure, mostly in the 1100-1300F temperature range. Gamma prime is not stable above about 1380F. A failure mechanism related to sensitization can occur in Incoloy 800H when it is thermally aged at 10001400F. In Incoloy 800H, this sensitization can contribute to premature failures due to preferential grainboundary oxidation.

Summary Materials of construction in sulfuric acid manufacturing plants generally include carbon steel, refractory- or brick-lined carbon steel, 300-series stainless steels, and Incoloy 800H. Carbon steel is used in cooler sections of the plant, typically at temperatures below about 900F. It may be coated for corrosion resistance. Refractory-lined or brick-lined carbon steel is used in the hottest sections of the plant, where temperatures typically exceed 1800F. Types 304 or 304H stainless steel are used for ducting that operates in the 900-1200F temperature range. Type 304H is typically preferred over Type 304 due to its better hightemperature strength. Stabilized stainless steels, such as Types 321 and 347, are candidates for expansion joint bellows. Incoloy 800H with restricted chemistry is the material of choice for expansion bellows operating above 1000F. Incoloy 800H should be ordered from a reputable manufacturer with a total limit on aluminum plus titanium content of 0.4-0.7 wt.% and grain size ASTM 2-5. Condensation of acids during shutdowns can cause significant corrosion of carbon steel and sensitized stainless steels. Steps should be taken to minimize the condensation risk, including gas purging and keeping metal temperatures above the dew point. Sensitized stainless steels are also subject to increased risk of stress-corrosion cracking from sulfur-based acids, and should be kept out of contact with condensing acids during shutdowns. All welded stainless steel is subject to chloride SCC if it contacts chloride-containing water during shutdowns. Post-weld heat treatment of welds at 1550-1650F (for 1 hour per inch of thickness, 1 hour minimum) will reduce the risk of chloride SCC.

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Table 1: Sensitization Characteristics of Common 300-Series Stainless Steels

Alloy 304 * 304L 321 347

Sensitization Temperature Range 750-1300F 850-1150F 900-1250F 925-1050F

Time Required in Sensitizing Range < 1 hr. > 100 hrs. > 10 hrs. > 1000 hrs.

* Type 304 with greater than 0.03 wt.% carbon, including 304H

Figure 1. The effect of sulfuric acid concentration and temperature on the corrosion rate of carbon steel above 60 wt.% acid. Below 60 wt.%, corrosion rate exceeds 200 mpy even at ambient temperature.