Carbon steel acid corrosion

Silicon used for diffusion treatment of carbon steels enhances corrosion resistance to sulfuric acid. Such a treatment has the surface durability of iron/silicon alloys without their marked brittleness. 

Table 3.35 Resistance of Fe-25Ni and carbon steel to corrosion by sulphuric acid...

Polymerization units use phosphoric acid as a catalyst in the reactor. Because solid phosphoric acid catalysts do not cause corrosion, carbon steel can be used. However, liquid phosphoric acid is very corrosive to carbon steel, so corrosion resistant materials are required. At a phosphoric acid concentration of 100%, type 304L SS is satisfactory up to 120 F (50 C), and type 316L SS is required from 120 to 225°F (50 to 107°C). 

Acid coolers are either anodically protected shell and tube design or non-anodically protected plate and frame design. Anodic protection can also be applied to carbon steel acid storage tanks (Corrosion Service, 2012). 

The presence of these acids in crude oils and petroleum cuts causes problems for the refiner because they form stable emulsions with caustic solutions during desalting or in lubricating oil production very corrosive at high temperatures (350-400°C), they attack ordinary carbon steel, which necessitates the use of alloy piping materials. 

Fluorosulfuric acid can be very corrosive. A study of the corrosive properties of fluorosulfuric acid during preparation and use showed carbon steel to be acceptable up to 40°C, stainless steel up to 80°C, and aluminum alloys up to 130°C (52). 

In aqueous solution, malic acid can be mildly corrosive toward aluminum and corrosive to carbon steel. Under normal conditions, it is not corrosive to stainless steels, which usually are the constmetion materials for processes involving malic acid. Malic acid is also virtually noncorrosive to tinplate and other materials used to package acidulated foods and beverages (Table 3) (27). 

In common with other hydroxy organic acids, tartaric acid complexes many metal ions. Formation constants for tartaric acid chelates with various metal ions are as follows Ca, 2.9 Cu, 3.2 Mg, 1.4 and Zn, 2.7 (68). In aqueous solution, tartaric acid can be mildly corrosive toward carbon steels, but under normal conditions it is noncorrosive to stainless steels (Table 9) (27). 

Shipment nd Stora.ge, Sulfur monochloride is minimally corrosive to carbon steel and iron when dry. If it is necessary to avoid discoloration caused by iron sulfide formation or chloride stress cracking, 310 stainless steel should be used. Sulfur monochloride is shipped in tank cars, tank tmcks, and steel dmms. When wet, it behaves like hydrochloric acid and attacks steel, cast iron, aluminum, stainless steels, copper and copper alloys, and many nickel-based materials. Alloys of 62 Ni—28 Mo and 54 Ni—15 Cr—16 Mo are useful under these conditions. Under DOT HM-181 sulfur monochloride is classified as a Poison Inhalation Hazard (PIH) Zone B, as well as a Corrosive Material (DOT Hazard Class B). Shipment information is available (140). 

Carbon steel is not normally a suitable piping material for concentrated sulfuric acid because of high corrosion rates in flowing acid. However, where temperatures and flow rates are low, heavy waU steel pipe is sometimes used for transferring product acid. 

Three commercial processes that use these various hot carbonate flow arrangements are the promoted Benfield process, the Catacarb process, and the Giammarco-Vetrocoke process (26—29). Each uses an additive described as a promoter, activator, or catalyst, which increases the rates of absorption and desorption, improves removal efficiency, and reduces the energy requirement. The processes also use corrosion inhibitors, which aHow use of carbon—steel equipment. The Benfield and Catacarb processes do not specify additives. Vetrocoke uses boric acid, glycine, or arsenic trioxide, which is the most effective. 

Chlorosulfuric acid attacks brass, bronze, lead, and most other nonferrous metals. From a corrosion standpoint, carbon steel and cast Hon are acceptable below 35°C provided color and Hon content is not a concern. Stainless steels (300-series) and certain aluminum alloys are acceptable materials of constmction, as is HasteUoy. Glass, glass-lined steel, or Teflon-lined piping and equipment are the preferred materials at elevated temperatures and/or high velocities or where trace Hon contamination is a problem, such as in the synthetic detergent industry. 

Corrosion. Aqueous solutions of citric acid are mildly corrosive toward carbon steels. At elevated temperatures, 304 stainless steel is corroded by citric acid, but 316 stainless steel is resistant to corrosion. Many aluminum, copper, and nickel alloys are mildly corroded by citric acid. In general, glass and plastics such as fiber glass reinforced polyester, polyethylene, polypropylene, poly(vinyl chloride), and cross-linked poly(vinyl chloride) are not corroded by citric acid. 

Solutions of citric acid are corrosive to normal concrete,aluniinum, carbon steel, copper, copper alloys, and should not be used with nylon. 

Although hydrogen cyanide is a weak acid and is normally not corrosive, it has a corrosive effect under two special conditions (/) water solutions of hydrogen cyanide cause transcrystalline stress cracking of carbon steels under stress even at room temperature and in dilute solution and (2) water solutions of hydrogen cyanide containing sulfuric acid as a stabilizer severely corrode steel (qv) above 40°C and stainless steels above 80°C. 

Carbon steel is easily the most commonly used material in process plants despite its somewhat limited corrosion resistance. It is routinely used for most organic chemicals and neutral or basic aqueous solutions at moderate temperatures. It is also used routinely for the storage of concentrated sulfuric acid and caustic soda [up to 50 percent and 55°C (I30°F)]. Because of its availability, low cost, and ease of fabrication steel is frequently used in services with corrosion rates of 0.13 to 0.5 mm/y (5 to 20 mils/y), with added thickness (corrosion allowance) to assure the achievement of desired service life. Product quahty requirements must be considered in such cases. 

The addition of small amounts of alloying materials greatly improves corrosion resistance to atmospheric environments but does not have much effect against liquid corrosives. The alloying elements produce a tight, dense adherent rust film, but in acid or alkaline solutions corrosion is about equivalent to that of carbon steel. However, the greater strength permits thinner walls in process equipment made from low-alloy steel. 

With some important exceptions, gray-iron castings generally have corrosion resistance similar to that of carbon steel. They do resist atmospheric corrosion as well as attack by natural or neutral waters and neutral soils. However, dilute acids and acid-salt solutions will attack this material. 

Virtually all metallurgies can be attacked by corrosive bacteria. Cases of titanium corrosion are, however, rare. Copper alloys are not immune to bacterial attack however, corrosion morphologies on copper alloys are not well defined. Tubercles on carbon steel and common cast irons sometimes contain sulfate-reducing and acid-producing bacteria. Potentially corrosive anaerobic bacteria are often present beneath... 

The corrosion rate of carbon steel (and most cast irons) in pure water is about constant between a pH of 4 and 10 (see Fig. 5.5). In solutions containing strong acids such as hydrochloric and sulfuric, normally pro-... 

Acidic attack on stainless steels differs from corrosion on nonsteunless steels in two important respects. First, nonoxidizing acid corrosion is usually more severe in deaerated solutions second, oxidizing acids attack stainless steel far less strongly than carbon steel. Hence, nitric acid solutions at low temperatures cause only superficial damage, but hydrochloric acid causes truly catastrophic damage. 

Hence, copper heat exchanger tubes handling acetic acid can he more seriously corroded at low temperatures than at high temperatures. Sulfuric acid at room temperature is handled routinely in carbon steel drums and tanks when water concentration is low, but it becomes extremely corrosive as water concentration increases. As ferric-ion concentration increases during acid cleaning of industrial systems, the corrosion rate of steel increases rapidly. 

Weld attack. Welds are often more susceptible to corrosion than other areas (see Chap. 15, Welds Defects ). Welds may contain porosity, crevices, high residual stresses, and other imperfections that favor attack. Carbon steel welds are usually ditched by acid attack (Fig. 7.10). 

The acid gases in the rich amine are extremely corrosive. The cono sion commonly shows up on areas of carbon steel that have been... 

Amine systems are extremely corrosive due to the acid-gas concentrations and the high temperatures. It is important that all carbon steel expo.sed to the amine be stress-relieved after the completion of welding on the particular piece. A system fabricated from stress-relieved carbon steel for DEA solutions, as recommended, will not suffer excessive corrosion. For MEA systems, corrosion-resistant metals (304 SS) should be used in the following areas ... 

Chloroaluminate laboratory preparations proved to be easily extrapolated to large scale. These chloroaluminate salts are corrosive liquids in the presence of protons. When exposed to moisture, they produce hydrochloric acid, similarly to aluminium chloride. However, this can be avoided by the addition of some proton scavenger such as alkylaluminium derivatives. In Difasol technology, for example, carbon-steel reactors can be used with no corrosion problem. 

Carbon dioxide produces a solution of carbonic acid (as in boiler condensate, see Section 53.3.2). Carbon steel is often employed but corrosion rates of up to 1 mm/yr can be encountered. Coatings and non-metallic materials may be employed up to their temperature limits (Section 53.5.6). Basic austenitic stainless steels (type 534) are suitable up to their scaling temperatures. 

In natural waters, cold-worked commercial carbon steels of the same composition corrode at more or less the same rate as annealed steels, presumably because the corrosion rate in this case is controlled by the diffusion of oxygen. Unprotected carbon steels are sometimes exposed to natural waters, and it is this latter situation which is of greater practical importance than the behaviour of steels in acids, since steels should never be used in these environments unless they are protected. 

The austenitic irons can be usefully applied in handling very dilute solutions of sulphuric acid at ambient or moderately elevated temperatures under conditions which can be very corrosive to ordinary cast iron and carbon steel. Austenitic irons have also given satisfactory service in handling... 

Table 3.50 Corrosion of Type I Ni-Resisi, casi iron and carbon steel in unaerated hydrochloric acid solutions at room temperature...

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