184 / Corrosion in the Petrochemical lndustry
Fluoroplastics are being increasingly used for
Polyvinyl chloride has excellent resistance
to H2S04 to approximately 93% concentration
at ambient temperature. Chlorinated PVC re-
sists slightly higher concentrations and tem-
peratures. ~hesématerialshave been used for
pipelines, but are not popular for longer runs,
because they have high coefficients of expan-
sion and require essentially continuous sup-
non. Manv comnanies orohihit the use of solid
;lastic piping ior safety considerations he-
cause of the notential for hreakaee.
Lined ~ i i ePolyvinylidene
. chliride (PVDC),
polypropylene (PP), polyvinylidene fluoride
(PVDF), and PTFE al1 are used for linings in pipe
for handling HzS04. The range of usefulness is
shown inTahle9. Although PP is shown as resis-
tant to 98% H2S04 at ambient temperatures, there
is considerable controversy on this point because
high concenuations can cause chaning and SCC.
Toavoidthis, thePPmust eitherbekeptincompres-
. . must be used.
sion or a cowlvmer
Polyethylene possesses a high degree of re-
.
sistance to aiiack b\ H?SOd
- . io 9 8 @concen-
. UD ~ encduniered a1 temDeraiJres io YO 'C (195 'F).
mtion at ambient temperature. The high-density
resins show virtually no attack in 98% acid at
temperatures to 50°C (120 'F). The use of poly-
ethylene equipment for handling HzS04 must be
resuicted to relatively low temperatures and low
loads unless continuously supponed. Polyethyl-
ene is widely used in laboratories for beakers,
bottles, and so on, which do not require heating
over direct flames. Tanks constnicted of molded,
seamless, high-density, cross-linked polyethyl-
ene have been used to store relatively smail vol-
umes (3800 L, or 1000 gal.) of concentrated
HzS04 up to 96%.
Fluoroplastics. Fully fluorinated plastics,
such as PTFE, fluorinated ethylene propylene
(FEP),and petiiuoroalkoxy (PFA), are unattacked
by HzS04 andoleum at al1 concentrations. Other
fluoroplastics, including PVDF, ethylene-chlo-
rotrifluoroethylene (ECTFE), and ethylene-
teuafluoroethylene (ETFE), are resistant to acid
up to98% concenhation, but haveless resistance
to oleum and SO3. Table 10 lists temperature
limitations and polymer designations.
Table 9 Suitability of plastic-linedpipingsys-
tems in H2S04
preferred for hot acid at concentrations above
H2S04 applications, such as linings in pumps
and valves. Sheet linings of FEP,ECTEE, and
PVDF pennit fahrication of large components,
such as tanks. Spaghetti-type FEP heat exchang-
ers have been used to cool concentrated H2S04in
contact plants for more than two decades. In
Europe, the heat recovered is often used for town
heating. These units cannot be used to cool
oleum, because the reaction of free SO3 and
. .
water vanornermeatine the FEP tubes causes ex-
cessive temperatures anddestnictionof theresin.
Recentlv. ..PFAconstnictionanddesienmodifica-
tions have improved exchanger temperature and
pressure capabilities. Dispersion of powder lin-
ings of PVDF, ECTFE, and PFA, with or without
fiber reinforcement, are applied toa broad range
of steel equipment (Ref 64). Equipment size is
limited only by available ovens.
Polyester Resins. Polyester and vinyl-ester
resins, nonnally used to form a fiherglass-rein-
forced laminate, show virtually no attack in di-
lute HzS04 at 90 OC (200 OF) and are used in
pi~.klingoprrationswhrre 15 lo 20% aciJ niay be
At 50% concentration, the polyesteri can be
safelv used to 65 'C (150 'F) and can even find
application in special cases where the tempera-
ture approaches 90 'C (220 "F). At 75% acid,
the temperature must be restricted to less than
65 "C (150 "F). At90%, mostpolyester andvi-
nyl-ester resins are rapidly degiaded even at
smbieni tempcrarurc\
Phenol-formaldehydeand furíural alcohol
resins are blended wiih reinfurcing glass orother
filler to make corrosion-resistant &nposite pipe
and equipment. Some phenol-fonnaldehyde
composites resist HzS04 at concentrations to
50% at 150 'C (300 'F), to 70% at 100 'C (212
OF), and to 96% at ambient temperature. Furfural
alcohol resin composites resist HzSO.1 atconcen-
trations to 50% at 90 "C (195 "F) and to 70% at
ambient temperature.
Carbon and lmpervious Craphite.
Impervious graphite has excellent corrosion re-
-
sistance to al1 but hiehlv< oxidizineu concentra-
tions of HzS04. Impewious graphite coolers are
used in 93% H-~ S O.(Ref
A. 65). Care must be taken
that the impregnant is resistant to the solution.
Polyester, furan, and PTFE impregnants are
available. Carbon is somewhat superior to graph-
ite in the higher concenUations and is generally
Table 10 Suitability of nonmetal linings in
H2S04
Mnxlmum
Material -C
bmpratum
'F
Has04
eonrrntrstion, %
FTFE 260
PFA 260
FEP 205
EffFE 150
ETFE 150
WDF 120 250 4 6
105 220 30-60
80 175 85-93
65 150 94-98
60%. Carbon is less conductive and lacks
suength and is therefore unsuitable for cooler
constniction. Both carhon and graphite are, of
course, brittle (Ref 66.67).
Coatings and Linings. Heat-cured phenolic
linings on steel are often used to prevent iron
contamination in 93% HzS04 and have reason-
able life in 98% HzS04 at ambient temperature.
These thin-film linings should not he used for
concentrations below 70%. because of ranid cor-
rosion of exposed steel substrate at pinho¡es.
Butvl mbber and Neonrene exhibit eood re-
sistance to 50% H2S04 at modest temperatures
and will resist 75% acid under ambient condi-
tions. A sulfonated chlonnated polyethylene
elastomer has heen successfully used in plant ap-
plications involving dilute H2S04 as well as
hoses handling 93% H2S04acid.
Glass and glass-lined equipment is widely
used in H2S04semice. For severe H2S04applica-
tions, glass-lined steel is apopular material of
construction.
Corrosion by Nitric Acid
Nitric acid is typically produced by the air
oxidation of NH3. This catalyzed reaction takes
place at very high temperatures. The gaseous
oxidation product is condensed to an aqueous
liquid of about 65% concentration. Dunng the
high-temperature oxidation, corrosion of the
plant materiais is of secondary concem. The ele-
- .
vated ooeratine temoeratures dictate that the
high-temperature propenies of the materials are
-
the nriman, desien consideration. Corrosion
considerations prevail during and after conden-
sation and at lower temperatures.
The concentration of HN03 up to 99% re-
quires secondary processing to remove excess
water. This involves múllng 65% HN03 with an-
other substance havine -
- a areater affinitv for
water (such as H2S04),then sepmthg the mixed
acids by distillation and condensation processes.
The basic materials of constniction used for
eauioment to c m out the vrocess described above
& iasonably stkdardized and are listed below:
Equipminl Mslerid
Ammonia con- Ausienitic stain1ess steei or nickel-
velfer base alloy
Acideoolcrs and Typ 3ML (avery low-earbon,0.030
condensers m.versionof type3M s&ess
EICCI)
65% acid storsgc Typ 3C4L
Acidconccnmtor Typ 3ML
Di~tillationcolumn
lincd stccl
-
Comsion-resistantcast imnor ~IBIS-
Conccnuatcd asid Aluminum:glassIPiFEIAlloy 610
condensers
Concentrared acid Aluminum dlay 3003, glas-lined stcel
siorage
Additional information is available in Ref 68 to 80.
Commerciallv nroduced HNO. is available in
concentrations fGm 52 to 99%. ~ i u i acidc over
 I in the Chemical Processing lndustry / 185

86% is described as fuming. Nitric acid up to unfommately, this advantage does not extend to precipitated axwund grain boundaries in the weld
95% is stored and shipped in type 304 stainless lower concenirations. HAZ. Because few pieces of industrial equip-
steel. Concentrated acid above 95% is handled in Nitric acid is a stmng oxidizing agent and ai- ment are made without welding, this is a serious
Aluminum Associahon (AA) aluminum d o y s tacks most metals, such as iron, by oxidizing the shortcoming. There are three methods of avoid-
1100 or 3003. Figure 43 shows the reason for metal to the oxide. A secondary effect of oxida- ing this problem:
this; the corrosion rate of type 304 stainless steel
increases rapidly above 95% concentration,
wbile that of aluminum 3003 remains essentially
tion 1s the generation of hydrogen at the met-
al/acid interface, whicb can cause hydrogen
embrittlement of some materials. for example,
.. Use low or extra-low carbon content (Fig. 46)
Add carbide s t a b i h r s to the alloy, as in types
constant to 100%. Anew stainless steel contain-
ing4% Si-alloy A-61&showsexcellentresis-
tance to concentrated HN03 (Fig. 44);
bigb-strength steels. Metals and alloys that are
able to form adherent oxide films, sucb as
austenitic stainless steels and aluminum alloys,
. 321 and347
Solution anneal after welding m reduce the
chromium carbide gradient
are protected by theu oxide ñlms from corrosion
by HNO,. .Of these altematives, solution annealing is
1.25 50
.
freanentlv not .
~ i z eal~oys
i
oractical. and the choice of stabi-
is not alwais an option. Therefore,
Metals
t when welding is planned, use of low-carbon
E 1'" 40 - .-
E Amtenitic Stainless Steels. The basic corro- stainless steels is the most popular altemative.
0.75 30 g sion data for the austenitic (300-series) stainless Sensitization of stainless steel refers to the
E
c steels have been reduced to the isocorrosion dia- precipitation of chromium carhides and the re-
.? 0.5 sultant depletion of the matrix of chromium as a
z .E gram format (Fig. 45). This diagram shows the result of heatingfrom480 to 760 OC (900 to 1400
5O 0.25 lo effect of temperature and HNOS concentration
u on the comsion of type 304 staidess steel. In- OE). Figure 47 shows that the effect of such heat-
o creasing either or both raises the corrosion rate; ing on wrrosion rate in 65% H N q is detrimen-
93 94 95 96 97 98 99 100 nevertheless, there is a large useful atea extend- tal in all cases. Sigma phase, wbich may also
ConcentrationO~HNO,.% ing from O tu 90% concentration and up to the form during prolonged heating of austenitic
stainless steels, is preferentially and rapidly at-
43 Compadmn oí corrarion oí aluminum alloy boilhg point below 50% concentration in which tacked by 65% HNO,. Solution heat treating the
3003 andtype 304 rtainleo rteel in HNO, the predicted corrosion rate is less than 0.13
mm/yr (5 milslyr). alloy will restore corrosion resistance.
Pxperience has shown that, although all The corrosion of austenitic stainless steels in
austenitic stainless steels behave in this fashion, HN03 is accompanied b& the formation of
Corrosian-resistant 3p"se 304 a n d 3 0 4 ~when
, welded, are clearly su- hexavalent chromium (Cr ), a complex chm-
perior to the others. Therefore, they are the most mium compoundthat increases the corrosivity of
popular grades for HN03 service. HN03 solutions. The effect of crsF buildup is
Figure 45 also applies in general to the cast sbown in Fig. 48 to be clearly dehimental. In
equivalents of wrought stainless steels.However, general, the presenee of cblorides and fluondes
'2 0.25 thegenerally highwarbon content of cast alloys in HN03 solutions tends to increase the corro-
and the propensity of castings to have high-carb- sion rate of stainless steels.
on surfaces often leads to selective intergranular Selective corrosion along grain boundaries is
O 20 40 60 80 100 corrosion in stmng HN03. common in austenitic stainless steels exposed to
ConcentrationofHNOS,% Although austenitic stainless steels are com- HNO,, especially strong acid. There is some evi-
of content the carrarion
monly used in HNO,, they are not without prob- dence to support the view that this cannot be en-
44 and imn-chromium-nickel ailoyr in boiling lems. One of the most prevalent is selective tirely prevented; bowever, maintaining low
HNOr Source: Reí 81 corrosion associated with chromium carbides carbon and avoiding sensitization will help.
For very concentrated acid (>95%), the addi-
tion of silicon to iron and to austenitic stainless
steels is beneficial. Cast uon with 14%Si is very
resistant to acid over 50% concentration. Re-
ceutly, iwo new stainless alloys of 4 and6% Si-
alloys A-610 and A-611-have been produced
(Ref 83). These new alloys have remarkable re-
sistance to HN03 above 95% (Fig. 44). At lower
concentrations, they offer no advantage over
type 304.
9- Aluminurn, as previously mentioned, shows
$ an advantage over type 304 at acid concentra-
tions exceeding 95% (Fig. 43). However, if acid
concentration falls below 80% or if kmperature
"O rises above 40 'C (100 OF), much higher c o m -
sion rates can be expected. This relationship is
clearly sbown in the isocorrosion diagram for
aluminum (Fig. 49).
The preferred aluminum alloys for HN03
service are alloys 1100 and 3003 (Ref 84). If
bigher strength is required. alloys 5052 or 5454
can be used.
Aluminum alloys may also suffer degrada-
Concantrstion of HNO,.% tion by improper welding or by using an incor-
rect ñiier metai, which leads to selective weld
~ 45 i ~Imcorro~i~n
. diagram forannealed type 304 rtainlerr rteel in HNOr Source: Reí42