3

The M e c h a n i s m of C O 2 Corrosion

The problem of C O 2 corrosion has long been recognised and has p r o m p t e d extensive
studies. Dry CO 2 gas is not itself corrosive at the temperatures encountered within
oil and gas production systems, but is so w h e n dissolved in an aqueous phase through
which it can promote an electrochemical reaction between steel and the contacting
aqueous phase. CO 2 is extremely soluble in water and brines but it should also be
r e m e m b e r e d that it has even greater solubility in hydrocarbons m potentially 3:1 in
favour of the hydrocarbon. Hydrocarbon fluids are generally produced in association
with an aqueous phase. In m a n y cases the hydrocarbon reservoir will also contain a
significant proportion of CO 2. As a result of this, CO 2 will dissolve in the aqueous
phase associated with hydrocarbon production. This aqueous phase will corrode
carbon steel.
Various mechanisms have been postulated for the corrosion process but all involve
either carbonic acid or the bicarbonate ion formed on dissolution of CO 2 in water
this leads to rates of corrosion greater than those expected from corrosion in strong
acids at the same pH. CO 2 dissolves in water to give carbonic acid, a w e a k acid
compared to mineral acids as it does not fully dissociate.
The steps of carbonic acid reaction m a y be outlined as follows:

CO2(g ) 4- H20 ---> CO2(dissolved) (1)

CO2(dissolved) 4- H 2 0 ¢=) H2CO 3 ~ H ÷ + H C O 3- (2)

The mechanism postulated by de Waard [2-4] is, perhaps, the best known:

H2CO 3 + e- --9 H + H C O 3- (3)

2 H --~ H 2 (4)

with the steel reacting:

Fe --9 Fe 2+ + 2e- (5)

and overall:

C O 2 + H 2 0 + Fe --~ FeCO 3 (iron carbonate) + H 2 (6)

Whilst there is some debate about the m e c h a n i s m of C O 2 corrosion in terms of

which dissolved species are involved in the corrosion reaction, it is evident that the
 The Mechanism of CO 2 Corrosion
resulting corrosion rate is dependent on the partial pressure of C O 2 gas. This will
determine the solution pH and the concentration of dissolved species.
In reality, the complete chain of electrochemical reactions is much more complex
than this brief outline. Depending upon which is the rate determining step the
dependance of the electrochemical reactions on pH and dissolved CO 2 varies.