Alloy Selection Guidelines: Chlorine, Hydrogen Chloride and Hydrochloric Acid
Introduction
Gaseous chlorine, at low temperatures and without moisture, is not particularly corrosive and is commonly handled in carbon steel. However, chlorine becomes aggressive to many metals if any water is present.
Similarly, dry hydrogen chloride (HCl) is not corrosive to most metals. However, hydrochloric acid, formed once dissolved in water, is corrosive to many metals and alloys.
These three substances, chlorine, hydrogen chloride, and hydrochloric acid, are discussed under various conditions. Materials considered include steels, stainless steels, nickel-base alloys, copper-base alloys, titanium, zirconium, and tantalum. Table 1 lists some nickel-containing alloys commonly in use and their UNS number.
Table 1: Nominal Composition of Nickel-Containing Alloys Used in Chlorine, Hydrogen Chloride, and Hydrochloric Acid Systems
Alloy | UNS Number | Ni (%) | C (%) | Cr (%) | Mo (%) | Cu (%) | Fe (%) | ASTM Spec (Plate) | ASTM Spec
(Seamless Tube and Pipe) |
Group I – C.P. Nickel and Nickel-Copper Alloys | |||||||||
200 | N02200 | 99.5 | 0.08 | – | – | – | 0.2 | B162 | B161 |
201 | N02201 | 99.5 | 0.01 | – | – | – | 0.2 | B162 | B161 |
400 | N04400 | 66.5 | 0.2 | – | – | – | 1.2 | B127 | B165 |
Group II – Chromium-Containing Nickel Alloys | |||||||||
600 | N06600 | 76 | 0.08 | 15.5 | – | – | 8 | B168 | B167 |
825 | N08825 | 42 | 0.03 | 21.5 | 3 | 2.25 | 30 | B424 | B163 |
625 | N06625 | 61 | 0.05 | 21.5 | 9 | – | 2.5 | B443 | B444 |
G-30 | N06030 | 42 | 0.01 | 29.5 | 5 | 1.8 | 15 | B582 | B622 |
G-35 | N06035 | 55 | 0.02 | 33 | 8 | – | 2 | B575 | B622 |
C-22/622 | N06022 | 56 | 0.01 | 21.5 | 13.5 | – | 4 | B575 | B622 |
C-4 | N06455 | 66 | 0.01 | 16 | 15 | – | 5.5 | B575 | B622 |
C-276 | N10276 | 58 | 0.01 | 15.5 | 16 | – | 5.5 | B575 | B622 |
59 | N06059 | 60 | 0.01 | 23 | 15.5 | – | 0.7 | B575 | B622 |
686 | N06686 | 56 | 0.01 | 21 | 16 | – | 2.5 | B575 | B622 |
C-2000 | N06200 | 57 | 0.01 | 23 | 16 | – | 1.5 | B575 | B622 |
Group III – Nickel-Molybdenum Alloys | |||||||||
B-2 | N10665 | 70.5 | 0.01 | – | 28 | – | – | B333 | B622 |
B-3 | N10675 | 63 | 0.005 | – | 30 | – | 2 | B333 | B622 |
B-4 | N10629 | 66 | 0.01 | – | 28 | – | 4 | B333 | B622 |
Austenitic Stainless Steels | |||||||||
304L | S30403 | 8 | 0.02 | 18 | – | – | Bal | A240 | A312 |
316L | S31603 | 10 | 0.02 | 16.5 | 2.1 | – | Bal | A240 | A312 |
800 | N08800 | 33 | 0.07 | 21 | – | – | Bal | A240 | B407 |
20 | N08020 | 33 | 0.02 | 19.5 | 2.2 | 3.2 | Bal | A240 | B729 |
6%Mo | S31254 | 18 | 0.01 | 20 | 6.2 | 0.7 | Bal | A240 | A312 |
6%Mo | N08367 | 24 | 0.01 | 21 | 6.2 | – | Bal | A240 | A312 |
6%Mo | N08926 | 25 | 0.01 | 20.5 | 6.2 | 1 | Bal | A240 | A312 |
7%Mo | S32654 | 22 | 0.01 | 24 | 7.3 | 0.5 | Bal | A240 | A312 |
Duplex Stainless Steel | |||||||||
2205 | S32205 | 5 | 0.02 | 22 | 3.2 | – | Bal | A240 | A790 |
a – UNS numbers beginning with an “N” indicate a nickel alloy, but the definition of a nickel alloy differs from that used by ASTM.
b – Most nickel alloys fall under the “B” specifications in ASTM specifications. However, due to a redefinition of a nickel alloy, a few alloys, such as 800
and 20 are being reclassified as stainless steel and included in the “A” specifications. That work is still in progress.
c – the 6%Mo alloys are a series of stainless steels, many of which are proprietary, all with roughly 6%Mo content and roughly equivalent in
performance.
Corrosion is a very complex process. Seemingly unimportant variables, such as small amounts of moisture, impurities, or metal chlorides, can completely change the corrosion picture. Various methods, such as graphs or tables, have been used to present corrosion data concisely. Using such published summaries, tables, and graphs alone is dangerous when selecting materials for industrial applications. They indicate which materials should not be exposed to a potentially corrosive environment.
Concise and condensed information is valuable in presenting an overall view of the situation. It can be used for screening purposes, thus minimizing the number of materials to be tested or considered. Summary figures of this type are presented in this publication to provide such overviews.
The standard design parameter for tubing, valve trim, and internals in chemical processes is about 0.1 mm/y (4 or 5 mpy) maximum corrosion rate. If the anticipated corrosion is uniform, an upper corrosion rate of 0.50 mm/y (20 mpy) may be acceptable for heavier wall vessels and pipes. If a corrosion allowance of 3 to 6 mm (0.12”- 0.24”) is applied under these circumstances, a safe life of six to ten years can be expected.
When localized corrosion, such as pitting, crevice corrosion, and stress corrosion cracking (SCC), which is characteristic of halide effects on many alloys, is anticipated, a corrosion allowance is inappropriate. A more detailed discussion of all aspects of materials selection for chlorine, HCl, and hydrochloric acid is available elsewhere.
PRODUCTION OF CHLORINE
Commercial chlorine is co-produced with caustic soda (NaOH) by the electrolysis of a sodium chloride solution. Sodium hydroxide is produced at the cathode, while chlorine is evolved at the anode.
Mercury Cells
Production of chlorine and caustic soda using mercury cells is rarely used, mainly because of environmental concerns. Rubber-lined carbon steel was the conventional construction material for mercury cell caustic. A fresh feed of about 25.5% sodium chloride brine diminishes to about 21% during electrolysis and is recycled to the cell for continued electrolysis. Chlorine is produced at the carbon or titanium anodes, while the mercury at the cathode forms an amalgam (Na/Hg). In a separate vessel, the denuder, the amalgam is reacted with demineralized water to obtain 50% NaOH of very high purity.
Alloy 400 (UNS N04400) and titanium or its variants have been used for the brine heaters. Titanium alloys are preferred because of the problem of liquid-metal cracking (LME). The nickel-base alloy is caused by entrained mercury and corrosion caused by small amounts of chlorine or hypochlorite.
Diaphragm Cells
In diaphragm cell electrolysis, an asbestos (or polymer-fiber) diaphragm separates a cathode and an anode, preventing the chlorine forming at the anode from re-mixing with the sodium hydroxide and the hydrogen formed at the cathode. The salt solution (brine) is continuously fed to the anode compartment. It flows through the diaphragm to the cathode compartment, where the caustic alkali is produced, and the brine is partially depleted. As a result, diaphragm methods produce an alkali that is quite dilute (about 12%) and of lower purity than mercury cell methods.
Membrane Cells
The membrane cell is analogous to the diaphragm cell except that the feed brine is more highly purified, and the perfluoro sulfone membrane has lower permeability than a diaphragm. This method is more efficient than the diaphragm cell, producing very pure caustic but requiring very pure brine.
CORROSION BEHAVIOUR – CHLORINE
The chlorine as produced is wet and thoroughly dried by contact with 98% sulphuric acid. It is then essentially non-corrosive at ambient temperature. Chlorine reacts with moisture to form a stoichiometric amount of hydrochloric and hypochlorous acid.
Cl2 + H2O —-> HCl + HOCl
These by-product acids are responsible for the unanticipated corrosion in many plant operations occasioned by moisture ingress.
Figure 1 guides the selection of various alloys for dry chlorine and indicates design parameters for tubes/internals and vessels/pipe components. The corrosion rates are based on relatively short-term tests and should be considered conservative.
The chloride coating on the metal surface tends to protect it up to a temperature level above which melting, vaporization, or decomposition removes such films. The corrosion rate appears proportional to the vapor pressure of the metal chlorides.
Carbon steel
Dry chlorine (Cl2) at ambient temperatures is typically handled and shipped in carbon steel, and corrosion is negligible. Usually, a more resistant alloy such as Alloy 400 or Alloy C-276 (UNS N10276) is specified for critical parts, such as valve trim, instrumentation, and orifice plates in chlorine pipelines. In contrast, wet chlorine is highly corrosive to steel and many nickel alloys and requires Alloy C-276 or titanium.
Carbon steel resists dry chlorine, and traces of moisture merely leave a film of ferric chloride. However, chlorine is a powerful oxidant; steel can ignite in dry chlorine, depending on its form and temperature. For example, steel wool or wire can ignite at as low as 50 °C (122 °F). Steel compressors are not specified above 110 °C (230 °F) since surfaces rubbing together can trigger ignition. Steel vessels are limited to a wall temperature of about 120 °C (250 °F) to 150 °C (300 °F) depending on specific application and company policy.
Carbon steel can be used up to 150 °C (300 °F) or even higher, up to about 200 °C (390 °F), if the equipment is appropriately cleaned first. Traces of chlorinated solvent contaminants can accelerate corrosion and increase the chance of ignition. Grease tends to react exothermically with chlorine and can increase the corrosion rate. When chlorine equipment is not in operation, proper shutdown procedures should be in place to keep the units dry or free from chlorine to prevent attack by wet residual chlorine on the steel.
Example of use
Ethylene is to be reacted with chlorine in the presence of a ferric chloride catalyst to produce ethylene dichloride (EDC). The reactor temperature is 60-100 °C (140-210 °F). The process is exothermic; water cooling removes the heat of the reaction.
Figure 1 indicates that carbon steel can be used for the reactor and auxiliary equipment, provided that the chlorine feedstock is dry and that proper temperature control is maintained by thoroughly mixing the reactants to prevent hot spots and runaway temperatures. Intimate mixing can be assured by using EDC as a reaction medium. Alloy 200 (UNS N02200) or Alloy 400 should be considered for reactor internals and critical components if experience shows the difficulty in controlling temperatures below 150 °C (300 °F) or operating above this temperature is desirable.
Stainless steels
As indicated in Figure 1, conventional 300 series austenitic stainless steels are inherently more resistant than carbon steels to dry chlorine. Stainless steels can be used up to 350 °C (660 °F) but are not often employed because possible ingress of moisture during shutdown can lead to chloride stress-corrosion cracking (SCC) or pitting corrosion.
Duplex stainless steels, such as Alloy 2205 (UNS S32205), resist dry chlorine, but HCl preferentially attacks the ferrite phase should moisture ingress occur.
Alloy 20 (UNS N08020) or the cast version CN7M valves are used in refrigerated, liquid chlorine equipment to resist corrosion in the moist chlorine gas that can form under ice on the metal surface. The bolting on valves for liquid chlorine is usually Alloy C-276.
Nickel and its alloys
Non-chromium-containing alloys, such as Alloys 200, 201 (UNS N02201), 400, and B-2 (UNS N10665), resist dry chlorine but are severely attacked if moisture ingress occurs.
Alloy 400 is commonly used as valve trim, but problems can arise with refrigerated systems. Any water below the dew point is corrosive to Alloy 400 and other nickel alloys.
Chromium-bearing grades such as Alloy 600 (UNS N06600) and Alloy C-276 (or its variants) are much better if contact with moisture is likely. Alloy C-276 is the standard valve stem material in carbon steel lines carrying dry chlorine since the stems can be in contact with humid air. Its more highly alloyed variants are not required but are equally resistant.
Alloy 200 and Alloy 600 are the alloys most commonly used for reactors, coils, agitators, and piping in the range of 250-500 °C (480-930 °F). A temperature of 500 °C (930 °F) is a prudent upper limit for nickel in dry chlorine. Alloy 600 is more robust than Alloy 201 and may be substituted.
Copper and its alloys
Copper alloys are not usually employed since acidic conditions rapidly attack them if moisture contamination occurs. Copper and its alloys will resist dry chlorine to about 200 °C (390 °F). Flexible, annealed copper tubing has been used for gas connections in some applications but must be replaced periodically for mechanical reasons.
Other metals
Titanium and its alloys will ignite and burn at temperatures as low as -18 °C (-0.4 °F) in dry chlorine and should never be exposed to liquid chlorine. Small amounts of water can passivate titanium; the amount needed to prevent attack varies with temperature. At room temperature, 0.2% is adequate, rising to 1% at 175 °C (347 °F). With water present, titanium is resistant and has been used for impellers introducing chlorine to organic syntheses. It has also been used in butterfly valves in non-metallic lines handling wet chlorine at ambient temperature. In crevices, the balance between HCl and HOCl, from the presence of moisture, may not be maintained, and severe corrosion may ensue.
Zirconium is resistant to dry chlorine at ambient temperatures but is corroded rapidly if water is present. It can erode at>1.3mm/y (>50 mpy) in chlorine-containing as little as 0.3% water at room temperature.
Tantalum resists wet and dry chlorine up to about 250 °C (480 °F), with 0 to 0.05 mm/y (0 to 2 mpy) rates. Breakaway corrosion occurs at higher temperatures, with rates of about 1.7 mm/y (66 mpy) at 300 °C (570 °F), and further increases in attack at only slightly higher temperatures.
CORROSION BEHAVIOUR – HYDROGEN CHLORIDE GAS
Figure 2 provides a guide to selecting various alloys in dry HCl gas. Upper corrosion limits of 0.075 and 0.50 mm/y (3 – 20 mpy) are shown as design parameters for specific components, and these are conservative limits.
(For example, some tests of 650 hours duration showed a rate of only 0.25 mm/y (10 mpy) at 590 °C [1,090 °F]). In operations above the dew point, moisture does not appreciably increase the corrosion rates. The hydrochloric acid formed by reaction with water will be highly corrosive at lower temperatures where moisture condenses.
It must be pointed out that there are many variables and that even small amounts of additives (e.g., agents to control catalyst activity) may influence the tenacity and vapor pressure of the protective corrosion scales.
Carbon steel
Carbon steel behaves in dry hydrogen chloride (HCl) like that in dry Cl2. It is usable up to about 250 °C (480 °F), above which another alloy, such as Alloy 200, is usually specified.
Stainless steels
Types 304L (UNS S30403) and 316L (UNS S31603) stainless steels are subject to chloride stress corrosion cracking (CSCC) below the dew point and during shutdown, even at ambient temperature. This can only be prevented if extreme precautions are taken to ensure a bone-dry feed to the unit and to maintain shutdown and start-up precautions of gas blanketing and keeping the unit dry.
Nickel and its alloys
The performance of Alloy 200 in dry and wet HCl gas has been consistently good. In cyclic operating conditions, particularly in the presence of air or oxygen, Alloy 600 and Alloy 825 (UNS N08825) offer good all-around resistance. Alloy 800 (UNS N08800) and Alloy 825 resist the CSCC phenomenon and have been used, respectively, for EDC pyrolysis furnace tubing and fluid-bed oxy-chlorination reactor internals.
Example
Ethylene is to be reacted with dry HCl gas and oxygen (O2) in the presence of copper chloride catalyst in a fixed-bed reactor to produce ethylene dichloride (EDC). The temperature is 275 °C (525 °F), and the pressure is 10 atmospheres. The process is exothermic; reaction heat is removed by the generation of steam on the shell side of the reactor.
Figure 2 indicates that stainless steel, Alloy 200, and Alloy 600 are candidate materials and resist dry and even moist hydrogen chloride. Usually, Alloy 200 is used for the reactor tubes; the tube sheets and heads of the reactor are clad with nickel on steel, and the interconnecting piping between the reactors is made of Alloy 200. Temperatures should be carefully controlled in this exothermic reaction because of by-product formation and deactivation of the catalyst above 325 °C (615 °F). Alloy 200 has an upper-temperature limit of 550 °C (1,020 °F), and with localized hot spots of, say, 750 °C (1,380 °F), catastrophic rates of corrosion and tube failure will occur.
Other metals
Due to a protective oxide film, titanium is resistant to dry hydrogen chloride gas at temperatures >150 °C (300 °F). Moisture present will cause corrosion and may produce hydrogen embrittlement.
Tantalum is resistant to dry hydrogen chloride gas up to at least 150 °C (300 °F). The metal is reportedly inert to hydrogen chloride gas containing water vapor to even higher temperatures.
CORROSION BEHAVIOUR – HYDROCHLORIC ACID
Hydrochloric acid is a critical mineral with many uses, including acid pickling of steel, acid treatment of oil wells, chemical cleaning, and chemical processing. It is used in more than 100 chemical manufacturing processes. It is sold in four concentrations, ranging from 27 to 37%. Pure acid is produced by reacting hydrogen and chlorine, the resulting hydrogen chloride being absorbed in water. However, It should be noted that most commercial acid is recovered as a by-product from organic syntheses and may have significant contaminants unless otherwise specified.
Hydrochloric acid is a typical reducing acid. It has a powerful inclination to form the azeotrope (or constant boiling mixture, CBM) with water. Exposed to the atmosphere, the concentrated acid tends to lose hydrogen chloride (while dilute acid loses water vapor) to become the CBM, 20.2% HCl.
Since hydrochloric acid is a reducing acid, the cathodic reaction is hydrogen evolution upon contact with metals below hydrogen in the electromotive series. Dissolved oxygen or stronger oxidants also promote the corrosion of many nonferrous metals above hydrogen. Figure 3 shows a general picture of appropriate alloy selection and immediately delineates the conditions suitable for handling with Alloy 400 and those where Alloy B-2 is required.
Carbon steels and cast irons
Hydrochloric acid is severely corrosive to steel over its entire concentration range. Specific commercial inhibitors can reduce the rate sufficiently to permit acid cleaning of process equipment (e.g., of rust or calcareous deposits) with 10-15% HCl.
Grey cast irons are also severely attacked, suffering graphitic corrosion, and are not amenable to inhibition. The austenitic nickel cast irons are more resistant, and certain high-silicon cast irons (e.g., 14.5% Si) are even more resistant.
Example
In a distillation process, entrained water forms dilute hydrochloric acid by the hydrolysis of chlorinated solvents when the stream is cooled below 125 °C (255 °F). Excessive corrosion will occur on carbon steel condenser tubing, piping, and the bottom of the accumulator.
Depending on the temperature and hydrochloric acid concentration, corrosion rates on carbon steel frequently run at 0.25 to 4.0 mm/y (10 mpy to 160 mpy). Ensuring a bone-dry system without inadvertent moisture pickup at flanges and seals or preventing water entrainment is tough. It should be noted that acid concentrations in such cases are mostly less than 0.5% and that, as Figure 3 shows, Alloy 400 can withstand such conditions satisfactorily.
Stainless steels
All kinds and varieties of stainless steel become active and are attacked by hydrochloric acid. The acid can cause pitting, crevice corrosion, or CSCC in deficient concentrations. With duplex grades, the tendency is to attack the ferrite phase preferentially. This phenomenon is also observed in some weldments.
Alloy 825 and Alloy 20 resist corrosion at all concentrations at temperatures <40 °C (100 °F).
The 6% Mo superaustenitic stainless steels, such as UNS S31254, UNS N08367, and UNS N08926, can be used in some applications in hydrochloric acid concentrations < 3 wt%. The 7% Mo superaustenitic stainless steel UNS S32654 with a nominal 7.3% Mo can be used up to about 8% acid at room temperature.
Nickel and its alloys
The chromium-free nickel Alloy 200 and Alloy 400 (and variants thereof) are attacked by hydrochloric acid only in the presence of dissolved oxygen or stronger oxidants. Cupric ions are also formed from the Alloy 400 to aggravate the attack further. An exception is the use of Alloy 400 in steel pickling operations, in which hydrogen evolution keeps all cations in the reduced state. Alloy 400 has been used at ambient temperature to reduce air-free systems by up to 20% (see Figure 3).
The 30% Mo materials, i.e., Alloy B-2, Alloy B-3 (UNS N10675), and Alloy B-4 (UNS N10629), were developed specifically for this service and resist all concentrations of HCl to the atmospheric boiling point. Dissolved oxygen is a mild accelerant; however, oxidizing contaminants (usually ferric ions, often derived from handling and storage) cause severe corrosion.
Alloy 600 is non-resistant to the chromium-bearing grades, suffering severe pitting and general corrosion. Those alloys that also contain molybdenum, as well as chromium, such as Alloy 625 (UNS N06625) and Alloy C-276 (and derivative compositions), are much more resistant in the presence of oxidizing contaminants than the Ni-Mo alloys but only at relatively low temperatures and concentrations. Alloy C-276, for example, has excellent resistance to all concentrations at room temperature and good resistance <0.5 mm/y (<20 mph) in all concentrations up to 50 °C (120 °F). Alloy G-30 (UNS N06030) and Alloy G-35 (UNS N06035) have reasonable resistance at ambient temperatures and are incredibly resistant to oxidizing chloride solutions, so they are resistant to hydrochloric acid contaminated with oxidizing salts.
Emission-control equipment is now becoming standard for removing HCl from various industrial gases. Corrosion in parts of this type of equipment can be very severe, and the attack rate is unpredictable. Alloys such as C-276 and high-chromium and low-iron variants such as C-2000 (UNS N06200) will find increasingly more comprehensive applications. In some cases, such alloys can be applied as thin sheet ‘wallpaper’ to a structural steel duct or scrubber, providing effective resistance at reduced cost.
Copper and its alloys
Theoretically, copper alloys (except for high-zinc brasses) should resist corrosion by HCl because they do not liberate hydrogen. In practice, dissolved oxygen produces cupric ions, which oxidize contaminants, and corrosion becomes autocatalytic. Unless the complete absence of oxygen or oxidizing agents can be guaranteed, copper and its alloys should not be used.
Other metals
For all practical purposes, titanium alloys are unsuitable for this service, although some grades (e.g., Ti-.15% Pd) are slightly more resistant than the unalloyed material. Even with meager corrosion rates, this metal tends to become embrittled by hydrogen absorption at cathodic sites.
Zirconium (e.g., R60702) tends to resist the liquid acid to well above its atmospheric boiling point (the CBM boils at about 110 °C [230 °F]), but the vapor-phase attack can occur. Also, there must be insignificant amounts of oxidizing contaminants (<50 ppm). Oxidizing contaminants can form pyrophoric corrosion products. Under pressure, zirconium can resist pure HCl at 120 °C (250 °F). Corrosion resistance can be reduced by the presence of cold work and by grain boundary precipitates associated with welds.
Of the reactive metals, tantalum is the most resistant to hydrochloric acid. In addition to unalloyed tantalum, specific tantalum alloys have been developed for improved strength and, in some applications, reduced cost.
Fluorides may be present in hydrochloric acid from some sources, significantly increasing corrosion rates in these metals. Zirconium will tolerate <10 ppm, while tantalum may tolerate ten ppm or more.
Summary of alloys for use in Hydrochloric Acid
Figure 4 shows a chart showing the indicated areas of use of various alloys. This chart suggests where corrosion rates should be acceptable or excessive and is based on field experience using commercial acid. It does not take account of economic factors or strength requirements for different applications. However, it is helpful as a first indicator of likely candidate materials to test or avoid.
Conclusion
In conclusion, selecting appropriate alloys for service in environments involving chlorine, hydrogen chloride, and hydrochloric acid is critical for ensuring long-term durability and operational efficiency. Given the aggressive nature of these chemicals, it is essential to consider factors such as corrosion resistance, mechanical properties, and compatibility with specific conditions of use. Alloys like Hastelloy C-276 and duplex stainless steels have proven effective due to their ability to withstand pitting and stress corrosion cracking. A thorough understanding of material properties and a strategic approach to alloy selection will help mitigate risks, enhance safety, and reduce maintenance costs in chemical processing applications. Investing in suitable materials is not just a choice but an essential strategy for operational success in demanding environments.