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H2S Corrosion in Refinery Materials

This document discusses H2/H2S corrosion in refinery processes. It describes the damage as uniform thickness loss and provides equations to calculate corrosion rates for various materials. Carbon steel is the least resistant, followed by Cr-Mo steels up to 9% Cr, then 400-series stainless steels, and most resistant are 300-series stainless steels. The equations factor in temperature, H2S concentration, and material. Affected units include hydroprocessing where corrosion may be severe downstream of hydrogen injection. Prevention includes using the equations to select resistant materials like 300-series stainless steel for piping and equipment.

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691 views9 pages

H2S Corrosion in Refinery Materials

This document discusses H2/H2S corrosion in refinery processes. It describes the damage as uniform thickness loss and provides equations to calculate corrosion rates for various materials. Carbon steel is the least resistant, followed by Cr-Mo steels up to 9% Cr, then 400-series stainless steels, and most resistant are 300-series stainless steels. The equations factor in temperature, H2S concentration, and material. Affected units include hydroprocessing where corrosion may be severe downstream of hydrogen injection. Prevention includes using the equations to select resistant materials like 300-series stainless steel for piping and equipment.

Uploaded by

BOB
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Refinery Materials and Corrosion

High Temperature H2/H2S Corrosion


2011

H2/H2S corrosion

description of damage and affected materials

Description of damage
presence of hydrogen in streams containing H2S influences
sulfidation corrosion at temperatures over 500F (260C)

Low Cr alloys are much less resistant to H2/H2S corrosion than for
H2-free sulfidation
generally uniform loss of thickness
corrosion rates in gas oil streams are higher than in naphtha streams

Affected materials (in order of increasing resistance)


carbon steel
Cr-Mo steels (i.e. 5Cr-1/2Mo and 9Cr-1Mo)
4xx series SS (i.e. 405 and 410)
3xx series SS (i.e. 304, 316, 321 and 347)

H2/H2S corrosion
critical factors

Carbon Steel Corrosion


in H2-Containing Naphtha

Couper-Gorman correlations were


developed to predict corrosion in
H2/H2S vapor streams from 400 1100F (205 - 593C) for different
alloys

Above specific temperatures and


below specific H2S concentrations the
reaction Fe + H2S FeS + H2 reverses
and corrosion should not occur

The equation for the No Corrosion


boundary is approximately

ln(mol%H2S) = 6.212ln(T(F)) 46.658

Cr-Mo alloys with up to 9 wt% Cr


provide only slightly better corrosion
resistance than CS

Partial condensation can increase


corrosion rates due to droplet
impingement

H2/H2S corrosion
critical factors

Equation for carbon and Cr-Mo steels

CR(mpy) FCrFG 2.681 10 5 e

10720
T 460

CH2S

0.15400.05891logCH2S

where:
CR = corrosion rate in mpy

FCr = alloy Cr content factor = 10-0.01900(%Cr)


FG = diluent factor (naphtha = 1.000, gas oil = 1.896)
T = temperature in F
CH2S = mol% H2S in process stream

H2/H2S corrosion
critical factors

Equation for 4xx and 3xx SS

CR(mpy) FT 2.8145 10 4 e

9644
T 460

CH2S

0.14645

where:
CR = corrosion rate in mpy

FT = alloy factor (4xx SS = 1.000, 3xx SS = 0.166)


T = temperature in F
CH2S = mol% H2S in process stream

H2/H2S corrosion

affected units or equipment

Piping and equipment in high temperature H2/H2S service in


hydroprocessing units such as hydrotreaters and hydrocracker units
Corrosion may be more severe downstream of hydrogen injection
points

H2/H2S corrosion
prevention/mitigation

Use Couper-Gorman curves to select resistant materials


Cr-Mo steels with up to 9 wt% Cr provide only slightly better corrosion
resistance than carbon steel
3xx SS alloys are highly resistant
use solid SS in feed/effluent heat exchanger tubes and piping
clad or weld overlay pressure vessels and heat exchanger shells,
channels, and tubesheets

H2/H2S corrosion
references

API RP 571, Damage Mechanisms Affecting Fixed Equipment in the


Refining Industry, Section 5.1.1.5
A.S. Couper and J.W. Gorman, Computer Correlations to Estimate
High Temperature H2S Corrosion in Refinery Streams, Materials
Performance, Vol 10, No 1, Jan 1971, pp. 31-37

NACE Pub 34103, Overview of Sulfidic Corrosion in Petroleum


Refining
API RP 939-C, Guidelines for Avoiding Sulfidation (Sulfidic) Corrosion
Failures in Oil Refineries

Check your understanding

F CR versus % Cr

The FCR as shown to the left varies


with Cr content. This shows minimal
reduction in corrosion rate as Cr
increases from 0 (carbon steel) to 9 %
(9Cr-1Mo).

This factor suggests that if the


corrosion rate of carbon steel is 10
mpy (0.25 mm/y) then 9Cr-1Mo would
corrode at about 7 mpy (0.18 mm/y).

Explain how this influences materials


selection for H2 + H2S environments
such as in Hydroprocessing.

1.2
1

F CR

0.8
0.6
0.4
0.2
0
0

6
% Cr

10

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