Sulfidic corrosion

Maxat Kokushev
Introduction

• Sulfidic corrosion is corrosion of metals and alloys by sulfur compounds at

high temperatures, usually in the range 230-540 Calcium degree.
• Corrosive or reactive sulfur compounds
• Elemental Sulfur (S8)
• Hydrogen sulfide (H2S)
• Mercaptans
• Organic sulfides
• Disulfides
• Polysulfides
Mechanism of sulfidation

• All sulfur compounds are not stable at high temperature (T>260 C) and are
decomposed to form H2S
• Hydrogen sulfide is more stable than sulfur-organic compounds and can
exist up to 650 C.
• This is explained by decrease polarity of bonds S-H and S-C in the row: H-S-
H>R-S-H>R-S-S-R
• Corrosion slows down as corrosion products (iron sulfides or rust) are
formed on iron surface and protect it from further corrosion.
Sulfide scale

• Sulfide scale is fragile and tends to crack and spall more readily
than oxides.
• Sulfidation is more destructive than oxidation by O2.
• Increasing chromium in iron, nickel, and cobalt base alloys
improves sulfidation resistance.
• The greater chromium content in alloy, the better its resistance
to sulfur compounds at elevated temperatures.
Mechanism of sulfidation

• Stability of sulfides can be arranged in the following sequence:

MnS>TiS>CrS>TiS2>FeS>Co4S3>NiS>FeS2
• Sulfidation Corrosion experienced in
• Preheat exchangers
• Furnace tubes
• Transfer lines
• Flash zone and bottom sections of columns
• Column high temperature draw off piping
Modified McConomy
Curve
• Sulfidic corrosion in
refinery units is
distinguished by
McConomy and
Couper-Gorman
curves.
Effect of temperature

• Sulfidic corrosion intensifies with increase of temperature from

230 C and reaches maximum at 425-450 C.
• Then corrosion rates of sulfidic corrosion decrease with increase
temperature till 540 C.
• At T > 425 C, nearly all quantity of corrosive sulfur already
reacted with metal surface and formation of dense coke
deposits can prevent further corrosion.
 The only realistic and practical way to control sulfidic
corrosion is to use corrosion resistant alloys containing
chromium.

Control Carbon steel can be used only till 260 C.

against
sulfidic Low-alloy 5Cr-0.5Mo steel is widely used up to around
343 C.

corrosion
Stainless steel containing 12% Cr is fully resistant to
sulfidic corrosion.

Austenitic stainless steels (SS 304,316,317,321) are

resistant to sulfidic corrosion.
Thank you!