Petroleum Refining and Petrochemical Operations/ 329
alloy 20 (N08020), alloy B-2 (N10665), and al-
loy C-4 (NlOOO2) or C-276 (N10276). For hy-
drocarbon streams containing only traces of
concentrated or dilute sulfuric acid, steel-body
valves with type 316 (531600) stainless steel
trim can be used. In this service, steel pump
casings that are weld overlayed with alumi-
num bronze have been successfully used.
Pump impellers made from high-silicon cast
iron are often used.
Piping for hy~ocarbo~acid mixing lines ahead
of the reactors may require alloy 20 (N08020), be-
cause water c o n ~ ~ ofofeed n stocks can cause
severe corrosion of car-bon steel. AUoy 400
(N04400) hasbeenfound tobeuseful forreactoref-
fluent lines around the caustic and wash-water in-
jection points. Valve trays in fractionation towers
require type 405 (S40500)or 410 (S41000) stain-
less steel tray valves and bolting. In general, organic
coatings are not resistant to concentrated sulfuric
acid. Teflon has excellent resistance to sulfuric acid
and is extensively used for gaskets, pump valve
packing, and mixing nozzles.
In addition to sulfuric acid, reactor effluent con-
tains traces of alkyl and dialkyl sulfates from w o n -
daty alkylation reactions (Ref 76). These esters
decompose in reboilers to form sulfur dioxide and
polymeric compounds (the latter are notorious fou-
lants). Sulfur dioxide corn^^ readily with water
in the upper part and overhead system of fractiona-
tion towers; the resultant sulfurous acid can cause
severe corrosion in overhead condensers. In some
units, carbon steel or admiralty metal ( C ~ 3
~fide.
tubes in overhead condensers, particularly those of
the d e i s o b u ~ tower,
r may have to be replaced
with alloy 400 (N04400) or titanium grade 2
( ~tubes. As~a rule, however,
j titanium is not
resistant to sulfuric acid corrosion. Neutralizers can
be injected into the overhead vapor limes of various
towers to maintain the pH value of aqueous conden-
sate near 7. Filming-amine~ r r o s i o inhibitors
n can
also be injected.
Caustic. Sodium hydroxide is widely used in
refinery and petrochemical plant operations to
neutralize acidic consti~ents.At ambient tem-
perature and under dry conditions, caustic can be
handled in carbon steel equipment. Carbon steel
is also satisfactory for aqueous caustic solutions
between 50 and 80 "C (120 and 180 O F ) , depend-
ing on concentration. For caustic service above
these temperatures but below approximately 95
"C (200 OF). carbon steel can also be used if it has
been postweld heat treated to avoid SCC at
welds. Austenitic stainless steels, such as type
304 (S30400), can be used up to approximately
120 'C (250 OF), while nickel alloys are required
at higher temperatures.
Severe caustic corrosion of the crude transfer
line, which is immediately downstream of the
caustic injection point, can occur in crude distil-
lation units when 40% (by weight) caustic solu-
tion is injected into hot, desalted crude oil to
neutralize any r e m ~ n i n ghydrogen chloride.
Predilutionof the caustic with water to form a 3%
(by weight) solution minimizes this problem.
Better dispersion of the more diluted solution in
the hot crude oil prevents puddles of molten
caustic from collecting along the bottom of the
transfer line. If caustic is injected too close to an beneficial. Filming-amine corrosion inhibitors
elbow of the transfer line, impingement by drop- are often ineffective. Several proprietary oxidiz-
lets of caustic can cause severe attack and hole- ing corrosion inhibitors based on sodium
through at the elbow. metavanadate are available. These have been
There are some unusual situations in which successfully used in certain cases, but licensing
caustic corrosion is encountered. For example, costs tend to be high for any but the smaller units.
traces of caustic can become concentrated in Regenerator towers usually should be lined
boiler feedwater and cause corrosion (gouging) with type 405 (S40500) stainless steel, and tower
and SCC (caustic embrittlement). This occurs in internals are often made of type 304 (S30400)
boiler tubes that alternate between wet and dry stainless steel. Where ~plicable, type 304
conditions (steam blanketing) because of over- (S30400) stainless steel is required for the rich-
firing. In some petrochemical processes, caustic amine pressure of the let-down valve, as well as for
gouging is found under deposits in heat exchang- piping downstream of the let-down valve, to control
ers that remove heat by generation of steam. For corrosion accelerated by high flow turbulence.
example, vertical heat exchangers for cracked Corrosion in the regenerator reboiler is usu-
gas in ethylene units are especially vulnerable if ally in the form of pitting and groove-type corro-
deposits are allowed to accumulate on the bottom sion of tubes and is caused by localized
tubesheet. Boiler feedwater permeates these de- overheating inside baffle holes {Ref 84). If ther-
posits and evaporates, and this causes the caustic mosyphon reboilers are undersized, part of the
to concentrate in any liquid that is left behind. tube bundle will become vapor blanketed, and
The caustic content of such trapped liquid can the tubes will overheat. Subsequent exposure of
reach several percent, which is more than enough the hot tubes to amine solution will cause severe
to destroy the n o ~ a l l yprotective iron oxide turbulence and velocity-acceleratedcorrosion. Va-
(magnetite) film on boiler steel and thus cause se- por blanketing also occurs if tubes an:allowed to fill
vere corrosion. partially with steam condensate; this reduces the
Amines. Corrosion of carbon steel by amines amount of tube surface available for heat transfer
in gas-treating and sulfur recovery units can usu- and increases the heat flux through the remainder of
ally be traced to faulty plant design, poor operat- the tubes. Unless faulty reboiler operation can be
ing practices, and solution c o n ~ i n a t i o n(Ref corrected, carbon steel tubes may have to be re-
77). In general, corrosion is most severe in sys- placed with type 304 ~ S 3 ~ or 0 316
0 ~ (S31600)
tems removing only carbon dioxide and is least stainless steel tubes. Alloy 400 (No4400) reboiler
severe in systems removing only hydrogen sul- tubes have been successfully used in amjne units
) Systems handling mixtures of the two fall thai handle only car-bon dioxide.
between these two extremes if the gases contain As a rule, carbon steel tubes are satisfactory
at least 1 vol% hydrogen sulfide. Corrosion in for regenerator overhead condensers. As dis-
arnine plants using mon~thanolamineis more cussed in the section "Sour Water" in this article,
severe than in those using diethanolamine, be- high corrosion rates can occur at this location,
cause the former is more prone to degradation. and carbon steel tubes may have to be replaced
Corrosion is not caused by the amine itself, with titanium grade 2 (R50400) tubes. Carbon
but is caused by dissolved hydrogen sulfide or steel tubes are used in reclaimers with proper
carbon dioxide and by amine degradation prod- neutralization of acidic constituents (Ref 85).
ucts (Ref 78). Corrosion is most severe at loca- Because the reclaimer can be taken out of service
tions where acid gases are desorbed or removed at any time, periodic retubing with carbon steel
from rich amine solution. Here, temperaturesand presents no problems. Cast iron pumps normally
flow turbulence are highest. This includes the re- are used in low-pressure amine service. If corro-
generator (stripper) reboiler and lower portions sion problems occur, high-silicon cast iron im-
of the regenerator itself (Ref 79). Corrosion can pellers can be used. In high-pressure amine
also be a significant problem on the rich-amine service type 316 ~S31600)stainless steel pumps
side of the leanhich-amine exchanger, in amine may be needed.
solution pumps, and in reclaimers. Hydrogen Phenol. Phenol (carbolic acid) is used in re-
blistering has been a problem in the bottom of the fineries to convert heavy, waxy distillates ob-
contactor (absorber) tower and in regenerator tained by crude oil distillation into lubricating
overhead condensers and reflux drums (Ref 80). oils. As a rule, all components in the treating and
The common material of construction for ra~inaterecovery sections, except tubes in
amine units is carbon steel. To prevent alkaline water-cooled heat exchangers, are made from
SCC, welds of components in both lean and rich- carbon steel. If water is not present, few signifi-
amine service should be postweld heat treated re- cant corrosion problems can be expected to occur
gardless of service temperature (Ref 81). in these sections. In the extract recovery section,
Postweld heat treatment also protects against hy- however, severe corrosion can occur, especially
drogen stress cracking. On the whole, there have where high flow turbulence is encountered. As a
been relatively few corrosion problems in most result, certain components require selective alloy-
amine units. ing with type 316 ( S 3 1 stainless
~ ~ steel. Typi-
Operating guidelines usually set limits on cally, stainless steel linersare required for the top of
arnine concentration (20%), acid-gas loading the dryer tower, the entire phenol flash tower, and
(0.35 mol per mole of amine), and reboiler steam various condenser shells and separator drums that
temperature (150 T, or 300 O F ) (Ref 82, 83). handle phenolic water. Tubes and headers in the ex-
These guidelines should be followed to minimize tract fumace should also be made of type 316
corrosion. Sidestream filtration is also extremely ( S 3 1 ~ stainless
} steel, with U-bends sleeved