High-Temperature Corrosion in Crude Distillation Unit and High Vacuum Unit

The first units of each oil refinery are crude distillation unit (CDU) and high vacuum unit (HVU) where
crude oil is distilled in two steps (at atmospheric pressure and at vacuum) into its major fractions.
There are a variety of corrosion mechanisms that play a role in these units and that usually have a very
different appearance at different locations. This summary focuses on the following main high-
temperature corrosion mechanisms in CDU and HVU hydrocarbon streams.

Sulfidation — Sulfidation or sulfidic corrosion is the reaction of steel and other alloys with reactive
sulfur compounds such as H2S from the fluid (e.g., crude oil) in high-temperature environments. Being
observed at temperatures above approximately 260°C, sulfidation corrosion rates increase with
temperature, peaking at approximately 450°C. Both carbon steel/low-alloyed steel and stainless steel
can be affected by this mechanism, which usually results in general wall thickness reduction. The
modified McConomy curves predict the influence of temperature, disclosing that increasing Cr and Ni
alloying contents in the bulk material can reduce corrosion rates significantly. This relation was
extended to hydrogen/H2Scontaining environments by the modified Couper-Gorman curves.
Dependent upon bulk material, flow conditions, and chemical composition of the fluid, the reaction
product iron sulfide (FeS) can form a stable, protective sulfide scale eventually reducing the corrosion
rate. But this passive layer can be damaged or even removed completely, which is influenced by flow
conditions, temperature, content/type of sulfur compounds and naphthenic acids, and hydrogen/H2S
content, etc. Moreover, a further influencing factor is the flow regime (e.g., two-phase and/or
turbulent flow) that can cause localized sulfidation. Influence of Mercaptans — In addition to H2S,
mercaptans (or “thiols”) are considered to be some of the most reactive and, hence, most corrosive
sulfur species. Their concentration depends strongly upon crude oil and boiling point range.
Experiments showed that mercaptans are most reactive somewhere between 235°C and 300°C where
they can accelerate sulfidation. Thus, particularly middle distillate loops, such as light and heavy gas
oil, are susceptible to mercaptan corrosion. A minimum mercaptan concentration of 100 ppm to 200
ppm was found to be necessary to enable mercaptan corrosion. Furthermore, it was suggested that
corrosion rates depend upon mercaptan type and that mercaptans start to decompose at
temperatures between 300°C and 400°C.

Naphthenic Acid Corrosion — Each crude oil contains naphthenic acids, where TAN is a common
measure of general acidity. Increasing TAN, temperature, and flow velocity/turbulences and
decreasing alloy contents of the bulk material accelerate naphthenic acid corrosion (NAC), which is
often found to be very localized. This corrosion mechanism usually occurs at temperatures > 220°C
and TAN > 0.5. The limit can be reduced to TAN > 0.1 for sweet, low sulfur crudes that have too little
sulfur available to form a stable FeS scale. As a consequence, it was stated that TAN (and thus the
overall acid content) is far too rough to evaluate the crude oil’s tendency to cause NAC. Molybdenum
contents > 2% in the bulk metal may restrict NAC corrosion rates, and it is argued that increasing
sulfur contents can inhibit NAC as a result of FeS scale formation. Furthermore, the reactivity of each
naphthenic acid, its distribution over boiling point range, and the influence of its molecular weight on
its corrosion behavior are still under discussion. For instance, experiments showed that naphthenic
acids start to decompose at temperatures > 350°C. As a result, NAC is difficult to predict and thus
observed frequently in CDU and HVU, particularly in furnace tubes and transfer lines between furnace
and distillation column. Several pipe ruptures in CDU or HVU furnaces, for instance, were caused in the
past by localized NAC. Those incidents can easily result in production losses of tens of million dollars.
The above chemical corrosion mechanisms can be further increased by erosion (by solid particles) or
erosion-corrosion (e.g., for very high flow velocities and/or droplet impingement). Both mechanisms
impair the FeS protective scale and accelerate sulfidation and naphthenic acid corrosion, in many
cases very locally. Particularly, transfer lines are susceptible to these effects because of the presence of
high flow velocities and two-phase flow. To control and limit high temperature corrosion, materials
and corrosion engineers usually consider one or several of the following approaches:

• Materials selection (by applying, e.g., corrosion resistant alloys [CRAs])

• Coatings (to protect the bulk material from the corrosive attack)

• Corrosion allowance (by increasing nominal wall thickness to allow a certain degree of corrosion)

• Corrosion inhibition (by injecting chemicals that, e.g., neutralize corrosive fluids)

• Process adjustments (by limiting parameters such as sulfur content, TAN, or temperature)

• Corrosion monitoring (by applying, e.g., nondestructive testing [NDT] to control the remaining wall
thickness)