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Senior Analyst and Inspector Training

H2SO4 ALKYLATION
May 2002
MATERIALS DEGRADATION IN H2SO4 ALKYLATION PLANTSCONTENTS
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SECTION 1TABLE OF CONTENTS

1.1 PROCESS INTRODUCTION _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1


1.2 CORROSION BY SULFURIC ACID _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 5
1.3 HYDROGEN BLISTERING _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 13
1.4 HYDROGEN STRESS CRACKING _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 15
1.5 BRITTLE FRACTURE AND AUTOREFRIGERATION _ _ _ _ _ _ _ _ _ _ 17
1.6 STRESS CORROSION CRACKING
BY CAUSTIC (SODIUM HYDROXIDE) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 25
1.7 CORROSION UNDER INSULATION (CUI) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 27
COMPONENT REVIEWCONTENTS
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SECTION 2TABLE OF CONTENTS

2.1 PIPING AND VALVES _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 1


2.2 SULFURIC ACID TANKS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 7
2.3 FEED COALESCER _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 11
2.4 STRATCO CONTACTORS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 13
2.5 FEED-EFFLUENT EXCHANGERS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 19
2.6 ACID SETTLERS AND COALESCERS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 21
2.7 ACID WASH DRUM _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 23
2.8 CAUSTIC WASHERS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 25
2.9 WATER WASHERS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 27
2.10 DEISOBUTANIZER SYSTEM _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 29
2.11 DEBUTANIZER SYSTEM _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 31
2.12 DEPROPANIZER SYSTEM _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 33
2.13 RERUN SYSTEM _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 35
2.14 SPENT ACID WEATHERING DRUMS _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 37
2.15 MISCELLANEOUS EQUIPMENT _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 39
1.1PROCESS INTRODUCTION
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1.1 PROCESS INTRODUCTION

T he classical alkylation reaction involves the chemical combination of a


saturated branched-chain hydrocarbon with an olefin. Combining isobu-
tane and butene (butylene), for example, produces iso-octane, a gasoline
component that is rated at 100 on the octane scale. In an alkylation plant, the two
major feed components are never pure; some side reactions always occur. As a
result, the reaction product (alkylate) contains a range of molecular weights and
molecular structures, which can be separated into heavy and light alkylate,
according to boiling point.
Alkylation plants can use either sulfuric acid or hydrofluoric acid as a catalyst.
But here we are only concerned with sulfuric acid. Although the catalyst acid is
not consumed in the alkylation reaction, with time it becomes diluted by water.
As a result, acid must be withdrawn regularly and replaced with a fresh supply.
Water enters with the hydrocarbon feed and the fresh acid feed. It is also one of
several byproducts generated by the alkylation process. Water removal is also
vital from a corrosion standpoint. The corrosion rate of carbon steel varies sig-
nificantly within the concentration range of 90-100% acid. At ChevronTexaco
plants, water is eliminated from the hydrocarbon feed through the use of Excelso

notes
dryers that simply coalesce the free water droplets and allow them to settle out.
Pascagoula Alky 2 used to use dryers that would remove the water dissolved in
the hydrocarbon, but those are now used elsewhere. Using the proper acid
strength and controlling reaction temperatures will minimize the amount of water
generated in the process.
In all ChevronTexaco plants, the acid and the two hydrocarbon streams are mixed
together and allowed to react in a Stratco Contactor. This is a horizontal vessel
with an internal heat-exchanger bundle to remove the heat of reaction and an end-
entering mixer to maximize acid and hydrocarbon contact. The cooling medium
(refrigeration) within the heat exchanger bundle is either flashed-process hydro-
carbon or freon from a separate refrigeration system. Figures 1.1-A and 1.1-B
show process flow diagrams for these two types of plants. Using hydrocarbon or
freon versus water for cooling avoids a potentially severe corrosion problem that
could arise if a tube were to leak and allow acid and water to mix.
Another type of alkylation plant uses what is referred to as Time Tank alkyla-
tion. Instead of Stratco Contactors, these plants use a reactor vessel, external
pump-around loop with circulating pump, with a heat exchanger in the loop to
remove the heat of reaction. ChevronTexaco has had no Time Tank plants since
the new alkylation plants in Richmond and El Segundo began operation in 1995.
Effluent from the Stratco Contactors or reactors is passed through a series of set-
tlers and coalescers to remove the acid, which is then recirculated to the reaction
system. The hydrocarbon phase is then washed to remove acidity before being
sent to the distillation system. Effluent wash is handled in several ways, depend-
ing on the plant design. Some plants use an acid wash to remove acid esters from
the net effluent and thus prevent deisobutanizer corrosion and fouling. The acid
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SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

wash is usually followed by an alkaline water wash. Other plants use a caustic
wash and water wash to remove acidity.
The typical distillation system consists of a deisobutanizer, debutanizer,
depropanizer, and often a rerun column. Isobutane is returned to the reactor loop,
propane and butane are sent to storage, and the heavy and light alkylate products
are tanked for eventual gasoline blending.
notes

12
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Figure 1.1-A. Alkylation Plant with Effluent RefrigerationUsed by All Refineries Except Pascagoula

13
1.1PROCESS INTRODUCTION
14
Figure 1.1-B. Alkylation Plant with External RefrigerationPascagoula
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION
1.2CORROSION BY SULFURIC ACID
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1.2 CORROSION BY SULFURIC ACID

Sulfuric Acid (H2SO4), a strong mineral acid that can be highly corrosive to both
metallic and non-metallic materials, is widely used in petroleum refining. No one
metal or alloy can be relied upon to resist H2SO4 under all conditions; corrosion
rates are affected by temperature, acid concentration, and turbulence.
Concentrated sulfuric acid is a strong oxidizing agent that readily attacks most
organic materials. A drop of strong acid placed on a piece of paper, wood, or
unprotected skin converts the organic material to little more than carbon, leaving No one metal or alloy
behind a black spot. Many, but not all, plastics and rubbers respond similarly to can be relied upon to
strong rather than weak or dilute acids. resist H2SO4 under all
conditions; corrosion
Sulfuric acid is made by generating sulfur trioxide (SO3) and then dissolving it in
rates are affected by
water:
temperature, acid
H2O + SO3 -> H2SO4 concentration, and
turbulence.
If every molecule of water combines with an SO3 molecule, what remains is
100% sulfuric acid. If some water molecules do not combine with the SO3, the
acid concentration is less than 100%. Most commercial applications have an acid
concentration in the range of 96-98% by weight. (Acid concentrations are almost

notes
always measured in weight percent.) When all water in a solution is converted to
sulfuric acid and then more SO3 is dissolved in the acid, fuming sulfuric acid
results. The sulfuric acid industry often uses terms like 20% fuming. Such
terms are not applicable in our industry, however, because we do not use fuming
sulfuric acid in our alkylation plants.
A clear understanding of the appropriate way to measure acid concentration is
essential to guarding against sulfuric acid corrosion. The concept that a solution
containing 50% (wt.) water and 50% H2SO4 is 50% sulfuric acid is simple. When
we are dealing with mixtures of acid and hydrocarbon, however, as we are in
alkylation plants, the subject of acid concentration becomes more complex. A clear understanding
Because sulfuric acid and hydrocarbon are not mutually soluble to any great of the appropriate way
extent, a mixture of acid and hydrocarbon will be two-phase. If we mix 50 to measure acid
pounds of 100% sulfuric acid with 50 pounds of hydrocarbon, we have a mixture concentration is
which is 50% H2SO4 by weight. But this mixture contains one phase of 100% essential to guarding
hydrocarbon and a second phase of 100% sulfuric acid. As a result, it corrodes as against sulfuric acid
if it were 100% acid. This two-phase behavior explains why we must measure corrosion.
sulfuric acid concentrations on an acid-water basis when dealing with cor-
rosion in alkylation plants.
Because process engineers have different concerns and may want to measure acid
concentration on a total rather than acid-water basis, we must take care to define

15
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

our terms in our discussions with them about corrosion. For example, assume that
a mixture contains:
50% hydrocarbon
40% H2SO4
10% H2O
A process engineer would say correctly that the acid concentration is 40%. For
corrosion purposes, however, the concentration is 80% sulfuric acid:
40/(40 + 10) = 0.8 = 80%.
Because spent sulfuric always contains dissolved hydrocarbons, there may be a
significant difference between acid concentrations on a total basis and those on
an acid-water basis. Unless you clearly understand this difference, your corrosion
predictions will be wrong and possibly dangerous.

Flange Quality CORROSION OF CARBON


Corrosion of Steel by
Sulfuric Acid
Specifications STEEL
0.15 Temp. 80-150F Carbon 0.25% Max.
Manganese 0.30-.60%
0.14 150F Phosphorus 0.05% Max. Carbon steel is commonly
Sulfur 0.05% Max.
0.13 used to construct sulfuric
Steel Completely Immersed 120F acid alkylation plants
0.12 Acid Not Stirred
Loss as Inches Penetration Per Year because it resists corrosion
0.11
Inches Penetration Per Year

from concentrated acid at


0.10 low (near-ambient) tempera-
0.09 tures. The relationship
0.08 100F between temperature, acid
0.07 concentration, and the corro-
sion rate of steel is shown in
0.06
Figure 1.2-A, the best infor-
0.05
mation published about
0.04 F
80F 150
F H2SO4 corrosion we have
120
0.03 120
F seen.
100
F
0.02 F 80
100 F F In Figure 1.2-A, notice the
0.01 80
great variation in corrosivity
0 that occurs in the 95-100%
50 52 54 56 58 60 61 62 63 64 65 66
concentration range. This
Baum
variation is critically impor-
tant to the alkylation process,
62 64 68 72 76 80 84 88 92 94 96 98 100
in which the strong acid
H2SO4, %
being used is gradually dilut-
ed by pick-up of water. As it
Figure 1.2-A. Steel Corrosion By Sulfuric Acid dilutes, it becomes progres-
sively less effective as a cata-
lyst for the alkylation reaction and eventually must be discarded. Clearly, the high-
er the initial acid strength, the longer the acid can be used. The tendency, then, is to
16 purchase the highest concentration acid possible in order to decrease consumption
1.2CORROSION BY SULFURIC ACID
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and improve plant economics. However, Figure 1.2-A tells us that 100% acid is far
more corrosive to steel than 98% and thus can cause a substantial increase in cor-
rosion rates. This increase is not purely theoretical; we have seen it in at least one
of our plants. Currently, all of our plants use higher strength acid than was used six
years ago.
Figure 1.2-B shows what happens at lower acid concentrations. Clearly, steel
does not have useful resistance to sulfuric acid at concentrations below 65-70%.

Figure 1.2-B. Effect of Sulfuric Acid Concentration


on the Corrosion Rate of Carbon Steel

Although the data represented in Figure 1.2-B is old, obtained at Richmond in


1949, it is accurate; the behavior of sulfuric acid remains unchanged.
Sulfuric acid reacts with steel to form a thin iron sulfate film on its surface. This
film erodes away at high fluid velocities, causing corrosion rates to increase
greatly. To combat corrosion:
Use long-radius bends in H2SO4 piping.
Limit velocities. Traditionally, the limit has been 3 ft. per second for carbon
steel, but this is under review.
Figure 1.2-A shows the effect of temperature on corrosion rates. At 98% concen-
tration, which we commonly see in alkylation plants, the indicated corrosion rates
are as follows:
5 mpy at 80F
10 mpy at 100F
20 mpy at 120F
30 mpy at 150F
Steel should generally not be used at temperatures greater than 100F.
Concentrated sulfuric acid is hygroscopic, i.e., it readily absorbs water from the
17
air and dilutes itself. Thus, if acid were to leak through valve packing, for exam-
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

ple, it would absorb water from the air, become dilute acid, and corrode equip-
ment from the outside. For more detail, see the chapter on piping and valves in
this manual.
Carbon steel in alkylation plants has not typically suffered from galvanic corro-
sion. We commonly line equipment with Alloy 20 and partially replace steel pip-
ing with Alloy 20 piping. Even at a steel to Alloy 20 junction, steel does not seem
to corrode at higher rates, provided that the weld profile does not introduce tur-
bulence. (Turbulence can result from the fact that Alloy 20 pipe is typically thin-
ner-wall than the adjacent carbon steel.)

CORROSION OF STAINLESS STEELS


The 400 Series straight chromium stainless steels, such as Types 405, 410, and
430, are less resistant to sulfuric acid than carbon steel and are rarely used.
Materials like Type 410, which are commonly used for valve stems and seats in
ordinary services, suffer unacceptably high corrosion rates in H2SO4.
The 300 Series austenitic stainless steels corrode at rates similar or worse than
carbon steel in the 20-85% range. The table in Figure 1.2-C shows published data
on stainless steel corrosion. Note that stainless steels containing molybdenum
(Types 316 and 317) have lower corrosion rates than the non-molybdenum grades
and much lower rates than carbon steel in concentrated acid. We occasionally use
T-316L stainless steel as an intermediate upgrade material, although Alloy 20 is
preferred.
In summary, we do not typically use stainless steels when acid concentrations are
above the point at which we measure acidity by pH. Stainless steels have limited
use for exchanger tubes in distillation overhead systems where trace acidity is
present. However, pitting on the cooling-water side is often a concern for stain-
less steel.

CORROSION OF ALLOY 20
Alloy 20 is the only alloy material used widely in alkylation plants, both as cast-
ings and wrought products. Historically, it has appeared under a variety of trade
names such as wrought Carpenter 20 or cast Durimet 20. Originally, the alloys
were 20% chromium, 29% nickel, 3% molybdenum, and 3% copper.
Shortly after development, 3% Cb was added to the wrought alloy in order to
decrease sensitization, or carbon precipitation during welding. In 1965, the
wrought alloy 20 was replaced with a newer version, Carpenter 20 Cb-3. The
newer wrought alloy has a slightly higher nickel content, 35% instead of 29%,
and all wrought material for sale today has the higher nickel content. The higher
nickel content gives the material added resistance to chloride stress corrosion
cracking.

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1.2CORROSION BY SULFURIC ACID
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Corrosion Rates Expressed in Inches Penetration Per Month

Rates at 100F Rates at 150F Rates at 175F Rates at 200F

% Type Type Type Type Type Type Type Type Type Type Type Type Type Type Type Type
Acid 304 310 316 317 304 310 316 317 304 310 316 317 304 310 316 317

- .0032 Nil Nil Nil .0183 Nil Nil Nil .0309 .0038 Nil Nil .0638 .0041 .0002 Nil

1 .0048 .0003 Nil Nil .0177 .0035 Nil Nil .0287 .0069 Nil Nil .0627 .0065 .0046 Nil

2 .0005 Nil Nil .0048 Nil Nil .0084 .0004 Nil .0092 .0067 .0049

3 .0055 .0005 Nil Nil .0326 .0057 .0007 Nil .0442 .0094 .0034 .0005 .1112 .0108 .0075 .0098

4 .0017 Nil Nil .0056 .0012 Nil .0108 .0048 .0005 .0130 .0083 .0121

5 .0137 .0022 Nil Nil .0939 .0072 .0032 .0004 .1286 .0137 .0069 .0075 .4504 .0143 .0120 .0199

6 Nil Nil

7 Nil Nil

8 Nil Nil

9 Nil Nil

10 .0294 .0162 .0007 Nil .1475 .1274 .0062 .0065 .3779 .2210 .0127 .0159 .4911 .2314 .0189 .0466

11 .0025 .0009

12 .0032 .0015

13 .0044

20 .0779 .0330 .0062 .0020 .4769 .2170 .0156 .0168 .9042 .4440 .0615 .0489 1.75 1.11 .1475 .0886

40 .0746 .0661 .0690 .0169 1.10 .3822 .5390 .2255 2.82 .7293 1.510 .8068 6.69 1.96 3.053 2.375

60 .1213 .1028 .2367 .2305 1.46 .7079 1.300 .9284 3.49 1.22 2.849 2.318 8.67 2.48 5.106 4.605

80 .0612 .0276 .0225 .0485 .1054 .1520 .0485 .0909 .1878 .5307 .0968 .2938 .6897 .8140 .3311 .5055

95 .0003 .0003 Nil Nil .0117 .0209 .0052 .0072 .0115 .0212 .0065 .0210 .0149 .0296 .0307 .0460

Figure 1.2-C. Sulfuric Acid Corrosion of Stainless Steels

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SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Figure 1.2-D shows isocorrosion curves for one of the trade name Alloy 20
materials, Durimet 20. In this chart, lines of constant corrosion rate have been
plotted on a temperature-concentration grid, a useful way to correlate the corro-
sion data, once it becomes familiar. Figure 1.2-D shows that Alloy 20 has good
resistance to all con-
centrations of acid at
350 ambient and near-
ambient tempera-
Durimet 20 tures. Because it also
300 resists high velocities,
Over Alloy 20 is common-
Boiling Point Curve 50 Mils
ly used for pumps and
250 valves in acid service.
Temperature, F

20-50 Mils
200 OTHER ALLOYS
20
50
5-20 Mils Although Hastelloy B
150 and C276 are not
5 often used, they have
0-5 Mils Per Year good acid resistance.
100 Their corrosion
behavior is shown in
Essentially Static Conditions Figures 1.2-E and
50 1.2-F, respectively
0 10 20 30 40 50 60 70 80 90 100
(next page).
Sulfuric Acid, % Generally, B is more
resistant to sulfuric
acid than C276.
Figure 1.2-D. Sulfuric Acid Corrosion of Durimet 20
However, B corrodes
more rapidly than
C276 in hot dilute acid. The Hastelloys are worth considering in locations where
Alloy 20 is attacked.
Lead also has good resistance to sulfuric acid. It was widely used in the old days
for vessel linings, before materials like Alloy 20 and the Hastelloys became avail-
able. Lead-burning is a lost artno one knows how to fabricate lead or lead-
lined equipment any more. The material is no longer used in acid service.
Copper alloys and Monel have useful resistance only in very dilute acids. They
may be useful for exchanger tubes in distillation overhead systems, where trace
acidity may be present.

110
1.2CORROSION BY SULFURIC ACID
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400
Over
200 Mils
350
Chlorimet 2
(Similar to Hastelloy B)
300 200
Temperature, F

Boiling Point Curve ls


50 0 Mi
20-5
250 20

200
5-20 Mils
5
150
0-5 Mils Per Year
100
Essentially Static Conditions
50
0 10 20 30 40 50 60 70 80 90 100

notes
Sulfuric Acid, %
Figure 1.2-E. Sulfuric Acid Corrosion of Hastelloy B

400
Chlorimet 3
(Similar to Hastelloy C)
350
Over
200 Mils
300
Temperature, F

Boiling Point Curve

250
200
20-50 Mils 50 50-200 Mils
20
200
5
5-20 Mils
150
0-5 Mils
Essentially Static Conditions
100
0 10 20 30 40 50 60 70 80 90 100
Sulfuric Acid, %
Figure 1.2-F. Sulfuric Acid Corrosion of Hastelloy C
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1.3HYDROGEN BLISTERING
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1.3 HYDROGEN BLISTERING

Hydrogen blistering is not widespread or particularly dangerous in sulfuric acid


alkylation plants. ChevronTexacos H2SO4 alkylation plants have had minimal
problems with the phenomenon. Nevertheless, because our competitors have
encountered it on rare occasions, analysts should be familiar with what causes
hydrogen blistering and what remedial measures can be taken.

Hydrogen blistering is a result of acid corrosion. The corrosion reaction produces


hydrogen atoms, some of them combining to form molecules of hydrogen gas
(H2) and others diffusing into the steel. When these atoms reach internal voids or
discontinuities in the metal, one hydrogen atom (H0) meets and combines with
another to form a molecule of hydrogen gas (H2). The hydrogen molecule is then
too large to escape by outward diffusion through the metal and is trapped in the
internal void. As time passes, more hydrogen molecules are formed, and the inter-
nal pressure in the void or discontinuity reaches a very high level (many thou-
sands of pounds per square inch). The cavity enlarges and distorts, becoming a
visible blister on the metal surface. Eventually the blister may crack through to
the surface, either around its periphery or across the middle.

notes
As blistering continues, cracks grow from one internal blister to another and ulti-
mately reach the metal surface. This phenomenon is called hydrogen-induced
cracking or HIC. Applied or residual stress, from welds, for example, may influ-
ence the direction in which HIC cracking grows. When this phenomenon occurs,
we call the result stress-oriented hydrogen-induced cracking or SOHIC.

Hydrogen blistering and hydrogen stress cracking (HSC) are both caused by the
presence of diffused hydrogen. The only difference between the two phenomena
is that blistering appears in a soft material and HSC in a hard material. However,
because methods of prevention are different, blistering and its related phenome-
na (HIC and SOHIC) are discussed here and HSC in a later chapter.

When purchasing new equipment, you can minimize potential hydrogen blister-
ing problems by specifying internal coating or alloy cladding. We have not
required the use of coating or cladding for the purpose of preventing hydrogen
damage in alkylation plants because it is such a rare occurrence. However, if we
had the unusual case in which we had to replace a piece of equipment that had
previously suffered blistering, we might want to require such precautions.

In some services, hydrogen blistering can be reduced or prevented by making


appropriate chemical changes to the environment. In FCC Units, for example,
polysulfides can be injected to remove cyanides. However, because no one knows
why blistering occasionally occurs in some sulfuric acid alkylation plants and not
in others, no chemical treatment or corrosion-control environment has been
developed. For this reason, and because blistering is rarely severe, a problem in
existing equipment is usually corrected by local weld repair. Maintenance people
making such repairs must be careful when cutting into blisters, especially large
ones, because the pressure can be extremely high. 113
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

The occasional hydrogen blister that appears in alkylation plants is most often
found in the sulfuric acid storage tanks. We are not aware, however, of any tanks
that have had to be replaced because of blistering. The fact that we see blisters
more often in tanks than in pressure vessels is probably because the tanks are
made of lesser-quality steels and contain more and larger laminations and non-
metallic inclusions.
notes

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1.4HYDROGEN STRESS CRACKING
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1.4 HYDROGEN STRESS CRACKING

Hydrogen Stress Cracking (HSC) is not a serious problem in sulfuric acid alky-
lation plants. Other than failures of B7 floating head studs, no HSC has been
found in ChevronTexaco alky plants to date. However, other companies have
found minor HSC cracking in strong acid service. Because HSC cracking in alky-
lation plants is rare and causes only minor damage, this discussion is provided
simply to increase awareness of the mechanism and its associated concerns.

HSC is not caused by corrosion penetration along the grain boundaries of the
metal and thus is not a true stress-corrosion cracking (SCC) phenomenon. Do not
confuse HSC and SCC; they follow different rules. In HSC, the hydrogen gener-
ated by aqueous corrosion of the metal diffuses into the metal in the form of
hydrogen atoms (H0) rather than hydrogen molecules (H2). If the metal is sub-
jected to applied or residual stress, the stresses tend to concentrate at the tips of
minor flaws or discontinuities. The hydrogen in the metal diffuses to these points
of stress concentration. The failure mechanism has been a subject of much
debate. For our purposes here, it is sufficient to visualize it as the high stress
pulling the metal atoms farther apart, making more room for the hydrogen. Once

notes
the hydrogen diffuses into this area, it stiffens the metal by reducing the ability
of the metal atoms to move in relation to each other under stress. The stiffened
metal then cracks instead of stretching and yielding. Cracks move in a series of
sudden, sharp bursts, the time between bursts being determined by how long it
takes hydrogen to migrate to the new crack tip.

In our industry, HSC typically occurs in aqueous H2S service. However, other
corrosive media, hydrofluoric acid (HF), for example, can cause similar failures.
These also fall under the general heading of HSC.

HSC can occur on carbon steel, high strength low alloys like 4140, chrome-moly
steels, precipitation hardening stainless steels (17-4 PH), and the 12 Cr and 17 Cr
alloys. Duplex alloys also sulfide crack but not as readily. The austenitic materials
like the 300 Series stainless steels, Inconels and Incoloys do not hydrogen stress
crack under any conditions we are likely to encounter. Metallurgically, crack-sen-
sitive materials are those with a ferritic as opposed to austenitic structure.

Soft steels, unlike hard steels, are not susceptible to HSC (the term steel in this
context referring to all materials with a ferritic structure). In general, cracking
does not occur on materials lower in yield strength than 90 ksi nor softer than
Rockwell C22. Note that strength and hardness are directly related. A steel of 90
ksi yield strength has a hardness of about HRC 22.

Defining crack susceptibility by strength and hardness is fine when dealing with
materials of homogeneous properties, such as a valve stem or pump shaft. It
becomes more difficult when we consider welds in plate or pipe, in which the
weld metal has a different hardness than the base metal. The weld heat-affected
zone has both a hard and soft band adjacent to the weld. In theory, we ought to
be able to prevent cracking by keeping base metal, weld metal, and weld heat- 115
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

affected zone below HRC 22. However, in practice, the hard band in the weld
HAZ is so narrow that conventional hardness measuring techniques cannot find
it. To avoid HSC in non-homogenous materials:
Avoid steels stronger than Grade 70.
Limit the hardness of the weld metal to 200 Brinell.
Be careful in selection of welding procedures.
Postweld heat treatment is a potent weapon for control of HSC. It reduces resid-
ual stress and softens the hard heat-affected zone of the weld. It is now common
to specify PWHT for all vessels in sour service, where HSC is common. Since
the phenomenon is not common in alky plants, PWHT is not necessary. In some
situations, however, PWHT may not totally accomplish the desired objectives.
Steels of high carbon equivalent (i.e., high in carbon, moly, or certain trace ele-
ments) do not respond to heat treatment. When buying a new column or vessel
for sour service, make sure that this question is reviewed by Materials Engineers.

On ordinary carbon steels, HSC appears only at welds. Cracks in high-strength


steels may appear anywhere, welded or not. In alkylation plants, valve trim is
usually Alloy 20 because valve stems of 12 chrome (e.g., T-416 machinable-
grade stainless steel) can crack. Hydrogen stress cracking is not a serious prob-
notes

lem in sulfuric acid alkylation plants. The occasional cracks that have been noted
have always been in strong acid service and have caused minimal damage. In
general, concerns with HSC in Alky Plants does not warrant putting HSC-sus-
ceptible equipment on Special Inspection Programs, as we do for equipment sub-
ject to sulfide stress cracking.

A few simple precautions provide adequate protection from HSC. New equip-
ment need not be stress relieved, except as required by ASME Code. PWHT of
welds is not required in the usual case. However, equipment that has been in acid
service may contain some dissolved hydrogen which can cause repair welds to
crack. Weld preheat should correct this problem. In those rare cases in which a
weld is highly restrained, a butt-weld patch in a vessel, for example, a 600F
bake-out prior to welding might be necessary to insure that all the hydrogen has
been removed.

As a further precaution, control welding procedures and consumables. Make sure


that weld metal hardness does not exceed 200 BHN. Historically, cracking has
occurred in spot-weld repairs in relatively thick walled equipment, where
restraint by the surrounding metal prevents the weld metal from shrinking as it
solidifies and cools. Also, the weld metal in a spot repair cools very rapidly,
which increases hardness. Again, weld preheat and the use of a low strength elec-
trode (60XX or 70XX) reduces cracking risk.

Floating head studs that will see acid exposure should be B7M versus the harder
B7 material.

116
1.5BRITTLE FRACTURE AND AUTOREFRIGERATION
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1.5 BRITTLE FRACTURE AND AUTOREFRIGERATION

See Sections 340-349 of the Corrosion Prevention Manual for a full discussion
of ChevronTexacos practices on prevention of brittle fracture.

Background When designing or testing metallic vessels and piping, we assume


that the metals are ductile, which means that if the metal is stressed beyond its
ability to deform elastically, it deforms plastically. It elongates or increases in size
as it decreases in wall thickness, failing after considerable noticeable deformation.
The assumption is incorrect for cast irons, for certain metals that undergo a duc-
tile-brittle transformation at low temperatures, and for metals that embrittle when
exposed to high temperatures. Cast irons are brittle at all temperatures and are
rarely used for pressure-containing parts in refinery service.

Many common metals used in petroleum refineries-most 300 Series stainless


steels (304, 316, 321, 347, etc.), copper alloys, nickel alloys, and aluminum
alloys-do not undergo a ductile-brittle transition at low temperatures. If 300
Series stainless steels contain significant amounts of ferrite, they can lose some
toughness at low temperatures. At low temperatures, carbon and low alloy
steels (also 12 Cr steels) become brittle; they fail without plastic deformation

notes
at stresses at or below the elastic yield strength.

Figures 1.5-A and B show the abrupt change in fracture toughness with temper-
ature, as measured in the charpy test. Carbon steel equipment needs to be above
its 15 ft.-.lb transition temperature in order to be safe from brittle fracture.

117
Figure 1.5-A. Charpy V-notch energy absorption of A36 steel
notes SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Figure 1.5-B. Charpy V-notch energy absorption of A516 gr. 70 steel

Factors Affecting Brittle Fracture The occurrence of brittle fracture of an


engineering structure such as a pressure vessel depends on three factors:
Presence of a flaw
Applied tensile stress
Material properties
The interdependence of these factors is shown in Figure 1.5-C (next page).

Per ASME code, brittle fracture is not considered a problem when the
applied stress is less than 8 ksi. Because the presence of defects is significant
in determining whether brittle fracture will occur, it is important to identify
and evaluate flaws and defects.

The effect of temperature on toughness of steel is shown in Figures 1.5-A, B, and


C. Thickness also affects properties-the metallurgical microstructure of
thicker materials is not as resistant to brittle fracture as thinner sections of
the same material. This is because thick materials have less enhancement of
properties from forming and heating. In addition, thickness is related to the effect
of stress; thicker sections have more inherent restraint. Conversely, brittle frac-
ture is not usually considered a problem for steel thickness below about one-tenth
inch.
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Susceptible Applied
Material Stress

BF

Flaw
Size
Identification and Evaluation of
Flaws is an Important Part of
Avoiding Brittle Fracture

notes
Figure 1.5-C. Interdependence of factors affecting brittle fracture

ASME Code and Industry Approach to Brittle Fracture Both pressure ves-
sel and piping codes require impact testing of specific materials if the metal
temperature is below a certain point. Because pressure vessels are often
thicker than piping and the consequences of a failure are usually greater, the
major concern about brittle fracture is with vessels. Figure 1.5-D (next page)
is a schematic depiction of the type of curves provided by the ASME Code and
API RP579 (see below). These curves show which materials can be safely used
at various temperatures without any special impact test requirements. Note that
both the type of material and the material thickness is important.

Minimum Design Metal Temperatures, Minimum Acceptable


Temperatures, Minimum Pressurizing Temperatures Currently the ASME
Code only relates to fabrication of new vessels or piping. A new API document,
RP 579 Recommended Practice for Fitness For Service contains an industry
standard for brittle fracture assessments of existing equipment. RP 579 uses the
same methodology as the Code, but some of the terminology differs, and it is
intended to apply to existing equipment.

The Code uses the Minimum Design Metal Temperature to designate the lowest
temperature at which the equipment can safely operate under significant stress
(more than 8 ksi). RP 579 uses the term Minimum Acceptable Temperature to
mean essentially the same thing. For years Chevron has used the term Minimum
Pressurizing Temperature, or MPT.
119
notes SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Figure 1.5-D. Similar to UCS-66 from ASME Section VIII, Division 1

The following table shows the maximum pressure that may be applied to pressure
vessels when they are below the MDMT or MPT.

ASME Design Code Yr Built Maximum Pressure Below MDMT

Section VIII, Div 1 Pre-1999 40% Max Allowable Working Pressure

Section VIII, Div 1 1999 & later 35% Max Allowable Working Pressure

Section VIII, Div 2 All 25% Max Allowable Working Pressure

Hydrotesting Warrants Special Precautions Many of the brittle fractures


experienced by the industry have occurred during hydrotest. ASME Code guide-
lines suggest that the mean metal temperature of equipment during hydrotest be
at least 30F warmer than the MDMT for the vessel. This added measure of safe-
ty is due to the fact that the hydrotest exposes the vessel to higher than design
pressure (1.5 times the MAWP for Section VIII, Division 1 vessels, and 1.25
times Design Pressure for Division 2 vessels), during which the risk of brittle
120
1.5BRITTLE FRACTURE AND AUTOREFRIGERATION
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fracture is increased. The mean metal temperature is typically controlled by con-


trolling the temperature of the hydrotest water.

Chevron practice agrees with the added 30F margin, except when it would cause
the hydrotest to be done at hotter than 120F. We avoid hydrotesting with water
warmer than 120F to limit the chance for burns to personnel in the event of a
leak or rupture. If there is a conflict between keeping the hydrotest temperature
cooler than 120F, but warmer than 30F above the MDMT, consult a materials
engineer.

Failures during hydrostatic test periodically occur when there is a lack of aware-
ness of the hazard of brittle fracture. An example is the failure of a carbon-1/2 Mo
steel heat exchanger channel during routine hydrostatic test (see Figure 1.5-E).
This vessel had been in service for 18 years. The failure took place at 50F and
3400 psig (test pressure was to be 4800 psig). Impact testing was not done at the
time of purchase. The Charpy V-notch impact strength of a sample from the failed
material was 3 ft-lbs. Fortunately, no one was injured; however, start-up of the
plant was delayed while the channel was repaired. The lesson to be learned is that
the potential for brittle failure should be carefully assessed before hydrostatic
testing is performed. For more information on preventing brittle fractures, refer

notes
to Section 520 of the Chevron Pressure Vessel Manual.

Fig. 1.5-E. Richmond Isomax TKC steam generator brittle fracture


121
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Autorefrigeration Heat converts liquid to vapor. The heat of a stove, for exam-
ple, boils water in a tea kettle. Some liquids (including water) vaporize at atmos-
pheric temperature, the heat required coming from the liquid itself. During this
process, the liquid cools, a phenomenon called autorefrigeration. If the liquid has
low vapor pressure, as water does, the effect is minimal. A dish of water left on the
kitchen sink cools itself to a few degrees below the temperature of the surrounding
atmosphere. On the other hand, liquids of high vapor pressure, such as ethane,
propane, butane, and anhydrous ammonia, cool to very low temperatures by
autorefrigeration.
Autorefrigeration in the Fluids with this property can be used as a refrigerants. Unfortunately, autore-
wrong place at the frigeration in the wrong place at the wrong time can cause materials failures
wrong time can cause through low temperature embrittlement.
materials failures Our goal is to construct piping and equipment out of steels that remain ductile under
through low temperature all possible operating conditions. We must consider not only normal operating tem-
embrittlement. perature, but also the possible cooling effects of autorefrigeration. The autorefrig-
eration temperature is defined as the temperature the contents of the vessel would
reach if the vessel were depressured to 40% of its MAWP (for ASME VIII, DN. 1
vessels). Get assistance from a process engineer to make this calculation. The
autorefrigeration temperature need not always be used as the minimum design
notes

metal temperature, because the loss of pressure that causes autorefrigeration also
reduces stresses on the vessel. However, failures have occurred where equipment
was re-pressured while still cold from autorefrigeration. The steel had adequate
toughness under the lower stress conditions during depressuring but not when full
pressure was applied.
Clearly, autorefrigeration is a concern only when handling liquids of high vapor
pressure. For practical purposes, these liquids include ethane, propane, and butane,
as well as the other C2, C3, and C4 hydrocarbon liquids. We need not consider
autorefrigeration when handling these compounds as vapors, because vapors do not
evaporate.
In refinery plants, deethanizers, depropanizers, and debutanizers must be evaluated
for potential autorefrigeration problems. Equipment must be constructed of steel
grades that remain ductile under autorefrigeration (depressurizing) conditions.
Normalized A516 or A537 is typically used.

Embrittlement Mechanisms Can Affect the MDMT of Alloy Equipment


Any time we encounter an embrittling mechanism which can shift the ductile to
brittle transition temperature of a material, we must carefully consider what is the
appropriate Minimum Acceptable Temperature (or Minimum Pressurizing
Temperature). For pressure vessel steels, the most relevant embrittling mecha-
nisms both affect low Cr steels:
Temper embrittlement
Carbide precipitation embrittlement
Temper embrittlement is caused by the diffusion of tramp elements such as P,
Sn, Sb, and As to the metal grain boundaries. This results in an upward shift in the
122 ductile-to-brittle transition temperature. The effect is greatest in early generation
1.5BRITTLE FRACTURE AND AUTOREFRIGERATION
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(pre-1970s) high strength 2-1/4 Cr steels, where the transition temperature shift
can be as much as 300F if they are operated above 650F. The effect is much less
severe in 1 Cr and 1-1/4 Cr steels and in low strength Class 1 materials. 1 Cr and
1-1/4 Cr steels also suffer from a carbide precipitation embrittlement phenomenon
if operated for extended periods above 900F.

For these reasons, 1 Cr and 1-1/4 Cr steels with low strength Class 1 properties are
assigned to the A (highest temperature) curve of Code section UCS 66. As fab-
ricated, these materials could have been assigned to the less restrictive B or C
curves by the manufacturer. For 2-1/4 Cr steels or for all Class 2 CrMo steels, con-
sult with an experienced metallurgist, and Section 300 of the Corrosion Manual.

notes

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1.6STRESS CORROSION CRACKING BY CAUSTIC (SODIUM HYDROXIDE)
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1.6 STRESS CORROSION CRACKING BY CAUSTIC


(SODIUM HYDROXIDE)

Sodium hydroxide (NaOH or caustic) and other highly alkaline hydroxides,


such as potassium hydroxide (KOH), can cause corrosion cracking of carbon
steel, low alloys, and stainless steels. These three classes of materials have simi-
lar resistance, but the higher-strength alloys are more likely to crack.

A true stress-corrosion cracking phenomenon (SCC), caustic cracking requires


both stress (either residual or applied), the presence of caustic, and an elevated
temperature. Very strong caustic solutions, such as 50%, crack steel at tempera-
tures above 110F. Somewhat lower concentrations, such as 20%, require at least
140F to crack. When solutions are very dilute, the temperature limit for crack-
ing is quite high and difficult to establish exactly. Remember, however, that in
certain circumstances heat can affect caustic concentration. Contact with a hot
surface evaporates water, for example, and increases the concentration in the
solution that remains. Caustic is non-volatile and does not evaporate with the
water, nor does it dry and form a non-corrosive salt deposit (as chloride salts do).

Caustic is used in alkylation plants to treat/neutralize certain product streams,

notes
most frequently LPG components. The treatment used to be performed at ambi-
ent temperatures. However, recently, the temperatures have been increased in
order to break down acid esters. Several sites have added heat exchangers to the
alkaline water wash recycle line, resulting in at least one incident of caustic stress
corrosion cracking. As a result, those lines are now PWHTed. Additionally, dur-
ing acid upset conditions, high quantities of acid may be carried into a caustic
washer, resulting in an increase in process temperature because of the heat gen-
erated during the neutralization process. Another process upset may cause caus-
tic carry-over from a caustic washer into downstream equipment, where temper-
atures may exceed the 140F cracking threshold. In either of these cases, non
post-weld heat-treated carbon steel may experience SCC, if the conditions are
right.

Heat-traced caustic lines may also cause problems. Welds may crack if the trac-
ing causes surface temperatures in excess of 140F. Therefore, traced caustic
lines should be stress relieved. Because caustic can also cause corrosion of steel
above 200F, the steam-tracing line must not contact the caustic piping directly.
Figure 1.6-A shows ChevronTexacos recommended limitations for carbon steel
in caustic service.

125
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

240
Area C - Carbon
Area C and Stainless
nt Steel Not
220
g Poi Adequate
lin
Boi NaOH
of Corrosion
200 and Cracking
Area B - Stress
Relief Recommended
180
Temperature, F

Cracking
notes

160

140
Area A - Stress
Relief Not
120 Required

100

80
0 10 20 30 40 50
NaOH, Wt %

Figure 1.6-A. Limits of Carbon Steel in Caustic Service

126
1.7CORROSION UNDER INSULATION (CUI)
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1.7 CORROSION UNDER INSULATION (CUI)

WHAT IS SUSCEPTIBLE?
Generally, any insulated equipment or piping which operates below about 300F
is susceptible to corrosion under insulation (CUI), as is equipment which oper-
ates intermittently in that range. Any situation that causes insulation to get wet
sets up a potential CUI condition. Driving rains or firewater deluges can thor-
oughly soak exposed insulation but just high humidity can chronically dampen
insulation so CUI problems are typically worse in warm, humid climates. Hotter
equipment tends to corrode less because heat dries the insulation.

Since practically the entire acid alkylation plant runs below 200F, CUI is a major
corrosion concern. CUI is especially a problem for refrigerated sections of the
plant. For equipment operating below ambient temperature, not only must entry
of liquid water be prevented but water vapor must also be excluded. On such
equipment, water vapor is pulled inward through the insulation and condenses on
the cold metal surface. This can be prevented by applying a vapor-tight insula-

notes
tion system. Vapor-tight systems are discussed in the section on insulation types.
However, the most important preventative for CUI remains maintaining good
coatings.

LOCATIONS OF WORST CORROSION


Corrosion is usually concentrated at low points where water settles, such as at 6
oclock positions on piping and horizontal vessels, low points in vertical piping,
and flanges (which run cooler and cause more moisture to condense). On vessels
with insulation support rings, water can collect above the rings if they are not per-
forated to allow water to drain out.

Damaged, punctured, or bulged weatherjacketing is another likely CUI location.


Poor installation or mechanical damage to weatherjacketing can allow water
to enter and keep vessel surfaces wet. During insulation installations, regular
inspections are necessary to identify and correct poor practices. Common weath-
erjacket defects are discussed in Section 731 of the Corrosion Prevention and
Metallurgy Manual.

Mechanical damage to weatherjacketing may result from people walking on it.


Using weatherjackets to support staging causes overlaps to open up and leads to
punctures. A commonly observed problem is splits in the joints of two-piece
insulation covers on ells. Weatherjacket damage requires early repair. Company
insulation specifications require higher-density insulation on top heads of
columns to reduce damage from walking. Soft insulations such as fiberglass and
mineral wool are not recommended for piping near ground level where it is most
likely to be walked on.
127
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

In the Reaction sections of Company alkylation plants, chilled piping and equip-
ment has historically seen severe corrosion. Stratco Contactors and associated
piping run cold and are subject to severe CUI, especially if the insulation is loose.
The refrigerant system in Hawaii has equipment and piping that is highly sus-
ceptible to CUI, including the refrigerant KO drum, Flash drum, and Suction trap.
Low point nozzles on the Acid Settlers have also been affected.

In both the Distillation and Reaction sections, CUI occurs in upper shell sections
and top heads of columns (which run cooler than bottom sections). Severe cor-
rosion has also been found along stiffener and insulation rings, and under dam-
aged weatherjacketing where water enters and soaks the insulation. Process lines
operating below 150F, such as fresh and spent acid lines, are highly susceptible,
as are areas where insulation stops and cold piping is open to the atmosphere.

Small bore connections to larger primary process lines are especially impacted
because they are thinner-walled to begin with. Instrument bridle piping is
impacted for this reason. At Pascagoula, small bore cold piping in the freon sys-
tem has historically had heavy corrosion under insulation.
notes

EFFECT OF CUI ON METALLURGY


For carbon steels and chrome-moly steels (up to 12 wt.% chromium), the main
concern is general corrosion and pitting loss. The CUI corrosion rate will depend
on the amount of water entering the insulation and its chemical composition.
Worst case examples of CUI usually involve damaged weatherjacket and/or chlo-
ride-containing water from sea spray, washdown water, or cooling tower over-
spray. Airborne salts are an important source of chlorides in coastal environ-
ments, especially within a mile from the shore.

Carbon and low-alloy steel exposed to the atmosphere will normally corrode at
about one or two mils per year (mpy), while corrosion under wet insulation can
be as high as 100 mpy, especially if chlorides are present. For austenitic stainless
steels (like Types 304 and 316), the bigger problem is chloride stress-corrosion
cracking (SCC).

In some insulation products, chloride salts are leached out once the insulation
gets wet. The Company has approved low-chloride brands of insulation which
have been tested to ensure a low leachable chloride content. See the discussion
below on types of insulation and the Insulation and Refractory Manual for more
details. ERTC Materials & Equipment Engineering (M&EE) can also provide
guidance on evaluation of new brands of insulation.

EXTERNAL COATINGS
Prevention of CUI includes maintaining weatherjacketing in good condition,
applying coatings to carbon steel and stainless steel vessels and piping, and
128
1.7CORROSION UNDER INSULATION (CUI)
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removing insulation where it is not needed. Expanded metal can replace insula-
tion in locations where personnel protection only is required.

Company specifications for new plant construction require that steel be coated
under insulation when process temperatures are not high enough to keep the insu-
lation dry. The temperature chosen depends on local weather conditions. Ideally,
all insulated equipment which operates more than 10% of the time at tempera-
tures below 300F should be coated. Plants in drier climates are less rigorous
about enforcing this guideline than those in humid climates.

Thin-film epoxy coatings are recommended for use on piping and vessels which
operate below 200F. Coating Systems 12.1, 12.2, 12.3, and 12.5 in the Coatings
Manual should be consulted for this type of service. Well-known brands, includ-
ing Ameron Amercoat 90HS, Carboline Thermoline 450, and Hempel Hempadur
1530 are listed for use below 200F.

Above 200F, epoxy coatings will soften and specialty coatings must be used.
The Thermoline 450 coating listed above is often used below 200F but can with-
stand temperatures up to 400F. Above 400F, polysiloxane coatings should be
used. Coating System 12.7 in the Coatings Manual lists Ameron 738. High tem-
perature coatings should also be used on equipment which requires steamout.

notes
Company Specification LZI alkyd primer, which was used for many years under
insulation cannot withstand steamout.

For existing plants, Pascagoula has had success wrapping corroded areas with
Denso wrap coating. Denso is relatively easy to apply, does not require much
clean up, and stops the external corrosion.

INSULATION TYPES
CUI is typically worst when fibrous insulations, such as fiberglass or mineral
wool, are used. Calcium silicate is better than fiberglass or mineral wool for pre-
venting CUI. The best insulation to use for CUI prevention is water-resistant cel-
lular glass or pearlite.

Polyurethane foam contains halogens which react with moisture to form acids,
making corrosion more severe. If polyurethane foam is used for insulation, it
must be closed-cell and a leaching test must be performed in which the resulting
water pH cannot be less than 3.5. Foam covering exteriors must be always be
covered with a waterproof mastic to prevent water entry. Foamed-in-place
polyurethane has problems in addition to corrosion, and is not recommended.
See Specification IRM-EG-3354 in the Insulation and Refractory Manual for
details.

For vapor barrier systems, Owens Corning Foamglas insulation is typically used
because the closed cells of the foam make it relatively nonporous. A troweled-
on barrier coating is used between joints in the foam glass. A fabric-reinforced
mastic is then laid over the exterior of the insulation. If protection against 129
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

mechanical damage is required, the mastic is covered with aluminum weather-


jacketing. See Company Specification IRM-EG-2634 on low-temperature insu-
lation for more details.

INSPECTION FOR CUI


Due to its localized nature, CUI can be difficult to find with random ultrasonic
testing (UT). Insulation removal is the best option where practical. When choos-
ing areas to strip, look for areas where water can get in to the insulation, such as:
support brackets, bolted-on instrument braces, and damaged weatherjacketing.

Successful inspection techniques also include UT measurements at cut-outs, spot


stripping of insulation plus UT wall thickness measurement, radiography, and
real time X-ray. See Company Inspection Strategy IS-19 and API 570 for more
information regarding inspection for CUI.
notes

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2.1 PIPING AND VALVES

VALVES FOR ACID SERVICE

A t one time, carbon steel valves with carbon steel trim were commonly used
in concentrated sulfuric acid service. On carbon steel valves with stainless
steel trim, the trim corroded faster than the carbon steel, leading to poor
performance. But even the all-steel valves suffered from a variety of problems:
Valve stems and seats corroded rapidly in throttling service
because of steels sensitivity to velocity-assisted corrosion.
Even valves that were normally full-open or full-closed could not
be relied upon to close tightly after extended service. Acid leaked
through the packing, absorbed water from the atmosphere, became
dilute, and caused external corrosion of the stem and valve body.
Rising stem valves pulled a thin layer of acid through the packing as
the valve was opened. This acid absorbed water from the outside
atmosphere, which caused some corrosion of the valve stem. The

notes
corrosion roughened the stem, which, in turn, damaged the valve
packing when the valve was operated. Acid leakage increased, as did
external corrosion of the valve.
Because of these problems, Alloy 20 has become the industry standard for valves
in concentrated sulfuric acid service. Experience with this material has been
excellent. Type 316 steel has also been used to some extent, and although it fares Alloy 20 has become the
better than carbon steel, it does not perform as well as Alloy 20. industry standard for
valves in concentrated
sulfuric acid service.
FRESH ACID PIPING
All ChevronTexaco sulfuric acid alkylation plants initially used carbon steel pip-
ing in fresh acid service. Piping standards require the use of long-radius bends
and limit fluid velocities to a maximum of 3 feet per second (or 1 meter per sec-
ond in plants using metric standards). This velocity limit is currently under
review and there is some evidence that a better limit is 1 fps. In the absence of
excessive velocity or turbulence, the life of steel has been adequate. Nevertheless,
we do encounter problems in two areas:
Turbulence cannot always be avoided. Even if the velocity limit is
followed, higher velocities may exist at reducers at pumps and at
control valves.
Recently, several plants have replaced piping in the fresh acid sys-
tems. As mentioned earlier, carbon steel corrodes more rapidly in
100% than 96-98% acid. The recent switch to stronger acid (plants
now specify 99.3% +/ 0.3%) may account for the corrosion. Use of
stronger acid decreases acid consumption in the plant, at the expense 21
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

of piping life. The cost savings of acid balance the decrease in pip-
ing life.
Our plants have all experienced corrosion in such turbulent areas as reducers,
tees, ells, pumps and control valves. In some cases, pump discharge spools have
failed in as little as one month. Replacing elbows with 5 diameter bends helps,
but the usual practice has been to upgrade selectively to Alloy 20 in areas that
show short life. Several plants have lowered the velocity by increasing pipe diam-
eters and upgraded turbulent areas to Alloy 20. Fresh acid piping, in all plants
except Burnaby, is a mixture of carbon steel and Alloy 20. At Burnaby, 316L is
being used in fresh acid service. Type 316L performs better than carbon steel, but
not at well as Alloy 20. It is an acceptable low cost choice for fresh acid service
only.

All piping welds are typically made using a GTAW (TIG) root pass to give a
smooth ID profile. SMAW (stick) welds can have drop-through, which creates
turbulence in the acid flow. The increased turbulence accelerates erosion-corro-
sion in and around the weld.
notes

Figure 2.1-A. Joint Detail for Welding Pipe of Unequal Thickness

When partially replacing steel piping with an alloy, you must consider the fact
that the alloy may be thinner than the steel to which it is connected, thus leaving
a shoulder or step at the junction between the two materials. Flow-induced tur-
bulence at this point greatly accelerates corrosion. Good practice is to bevel the
thicker steel side before making the connecting weld so that the weldment is
made between two metals of equal thickness. Figure 2.1-A shows the desired
joint detail for welding pipe of unequal thickness.

Typical inspection methods for piping include ultrasonic (UT) thickness gauging
and radiography. Given the localized nature of sulfuric acid corrosion, UT may
not find the thinnest areas. Radiography may be more useful to help identify pipe
22
2.1PIPING AND VALVES
ERTC
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thinning in selected areas, e.g., weld heat-affected zones, elbows, downstream of Given the non-uniform
elbows, and other areas of turbulence. nature of sulfuric acid
corrosion, UT may not find
Flow-induced corrosion may not always appear at the first elbow after a long,
the thinnest areas.
straight run of piping. Elbow corrosion has been found to be more severe after
Radiography may be more
multiple, closely-spaced changes in direction. In many cases, the straight section
useful to help identify
of pipe just after an elbow has the worst corrosion because of the elbow-induced
pipe thinning in selected
turbulence. Therefore, thoroughly inspect elbows and adjoining downstream pipe
areas, e.g., weld heat-
when multiple changes in direction are encountered.
affected zones, elbows,
Hydrogen grooving (or hydrogen tracking) of carbon steel fresh-acid piping can downstream of elbows,
occur in pipes where acid is slow-moving. Corrosion is typically at the 12 oclock and other areas of
position. See the discussion of hydrogen tracking in the Tank section. suspected turbulence.

SPENT ACID PIPING


Carbon steel performs even more poorly in spent acid service than in fresh,
although a significant amount of steel remains in service. The worst corrosion
appears in areas of high velocity or turbulence, as it does in fresh acid service.
Many of the fresh-acid concerns and inspection methods discussed above are the

notes
same for spent acid even though the corrosion potential is higher. Selective cor-
rosion has been found at weld heat-affected zones. The usual materials upgrade
is, again, Alloy 20, although type 316 has been used on rare occasions with mod-
est success. However, as in fresh acid service, we most often find a mixture of
carbon steel and Alloy 20 piping. In straight lengths of piping, steel may last from
5 to 10 years. In turbulent zones, failure may occur in a few months.

ACID-HYDROCARBON LINES (CONTACTOR EFFLUENT, ETC.)


Acid-hydrocarbon lines around the contactors and settlers see hydrocarbon with
entrained acid. Consequently, carbon steel corrodes less here than in acid alone.
Corrosion of steel appears in high velocity or turbulent areas, where carbon steel
is occasionally upgraded to Alloy 20. The extent of corrosion depends greatly on
the amount of acid carryover and operating temperatures. The first failures are
likely to occur in pump suction and discharge spools within about 2 years. In
some plants, the first piping failures occurred after 10 years.

Drains and other dead legs corrode at a higher rate than flow lines because acid
tends to separate from the hydrocarbon and collect at low spots.

Because of the low operating temperature of these lines, corrosion under the insu-
lation (CUI) can be aggressive. The older plants have had significant metal loss
due to CUI.

One mix point, where failures have occurred, is where the refrigerated effluent
mixes with the fresh hydrocarbon before entering the contactor. The effluent con-
tains acid which combines with water in the feed to cause corrosion. 23
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

ACID WASH PIPING


The majority of the acid recirculation piping in most plants with acid washer
drums was initially constructed of carbon steel. Usually Alloy 20 is installed
where the recirculated acid is mixed with reactor effluent and from the injection
point to the acid wash drum. Some plants have experienced significant corrosion
of the carbon steel in the acid circulation piping and have upgraded to Alloy 20
in these areas. In the highly corrosive mix area, Alloy 20 has performed well.
However, the mixing T will suffer from localized corrosion due to turbulence and
localized acid dilution. The corrosion rate is typically 3-4 mpy, but the area with
the highest corrosion rate can be difficult to detect. It is recommended that these
Ts be inspected by x-ray.

CAUSTIC WASH PIPING


Corrosion of caustic recirculating lines is common. It is even worse in the caus-
tic mixing spool. In all plants, the mixing spool has either been originally fabri-
cated with Alloy 20 or upgraded later. In some cases, the Alloy 20 spool has expe-
rienced corrosion severe enough to warrant its replacement. Other mixers, includ-
notes

ing Kynar and Teflon-lined carbon steel have been tried unsuccessfully.

The problem is caused by acid carry-over from the settlers. Low alkalinity makes
the circulating caustic solution unable to neutralize the acidity completely under
upset conditions. The result is a transient excursion of the caustic solution onto
the acidic pH side.

WATER WASH PIPING


Water wash circulation lines corrode for the same reason as the caustic washer
piping. The worst corrosion has occurred at the mixing spool, requiring replace-
ments in some plants in as little as 2 years. Alloy 20 has been the common
replacement material. The water recirculation lines sometimes corrode at rates as
high as 100 mpy. Some plants have experienced numerous failures in the weld
zones. Line replacement is common. In some cases, Alloy 20 piping has been
installed in the turbulent zones at the inlet and/or outlet of the circulating pump.

DEISOBUTANIZER, DEBUTANIZER, AND DEPROPANIZER PIPING


For the most part, this piping does not corrode at significant rates. In those few
cases where replacement was needed, the piping had performed well for 30 years
or more. Some plants experience mild corrosion in the overhead of the distilla-
tion columns. This mild corrosion is usually found between the condensers and
the overhead reflux drum. Corrosion may also be found in the reflux drum
process water-blowdown piping. Most corrosion is attributable either to acid
24 upset or breakdown of acid esters in the column reboilers.
2.1PIPING AND VALVES
ERTC
CONFIDENTIAL

With effluent-cooled plants, corrosion in the depropanizer overhead may be par-


ticularly severe if the depropanizer feed is not properly treated with caustic to
remove SO2. Without proper treatment, the SO2 converts to corrosive sulfurous
acid (SO3) and causes depropanizer overhead corrosion.

PACKING AND GASKETS


Currently, most of our sulfuric acid alkylation plants use raised face flanges with
spiral-wound gaskets. The gaskets are Teflon-filled, with Alloy 20 windings. The
outer centering ring is carbon steel. However, one plant claims to be using blue
asbestos rather than Teflon in their spiral-wound gaskets. The usual valve pack-
ing material for concentrated acid service is Teflon. Most common at present is
the braided Teflon, free of graphite binders, such as John Crane 1045.

notes

25
2.2SULFURIC ACID TANKS
ERTC
CONFIDENTIAL

2.2 SULFURIC ACID TANKS

Tanks storing concentrated (96-100%) sulfuric acid are normally constructed of


carbon steel. If the proper design and operating precautions are followed, tank
life is generally good. The chemical industry group within the National
Association of Corrosion Engineers (NACE) has been working to develop stan-
dards for the design and construction of sulfuric acid tanks. To control general
corrosion, NACE recommends the following:

88-99.5% H2SO4 Carbon steel with 1/4 corrosion allowance

99.5-100.5% H2SO4 Type 304 or 316 stainless steel

Over 100.5% H2SO4 Carbon steel with 1/8 corrosion allowance

Of special interest here is the need for alloy tanks for acid in the 99.5-100.5%
concentration range. In recent years, to decrease acid consumption, the plants
have started using stronger acid. The current best practice requires acid strength
to be 99.3% +/ 0.3%. Even though the acid concentration can now be above
99.5%, we still use carbon steel to store fresh acid. As a result, established cor-
rosion rates for fresh acid tanks are likely to be misleading. There is also the pos-
sibility of higher corrosion rates in carbon steel piping and equipment.

One corrosion phenomenon unique to sulfuric acid is hydrogen tracking. Acid


corrosion, even at very low rates, generates hydrogen, which evolves at the metal
surface in the form of small bubbles. In a tank manway or horizontal nozzle, the
hydrogen bubbles rise to the top, move along the upper side of the nozzle, and
then rise along the tank shell until they escape at the liquid surface. Steel is pro-
tected against sulfuric acid corrosion by a film of iron sulfate. However, the
movement of hydrogen bubbles along the metal surface gradually erodes the sul-
fate film and causes grooving corrosion. In an acid tank, corrosion grooves can
Acid tanks should be
appear along the top of manway necks and horizontal nozzles, and vertical
inspected every 5 years.
grooves can appear in the tank shell, leading upwards from the nozzles or man-
The inspection should
ways. If horizontal vessels happen to be used for acid storage, hydrogen groov-
include both a visual and
ing can be expected along the top inside surface. Figure 2.2-A shows hydrogen
UT examination of the top
grooving at the top of a tank nozzle.
of manways and
Using a liner of alloy or thick carbon steel in horizontal nozzles and manways can horizontal nozzles for
prevent hydrogen grooving in vertical tanks. The liner covers only the top 180 detection of grooving.
degrees in manways, but in nozzles a 360 degree liner is easier to install. In either
case, the liner should extend a short distance into the tank beyond the inner wall.
The goal is to direct the hydrogen bubbles away from the tank wall so that they
can rise to the surface without eroding the iron sulfate protective film.

Hydrogen grooving occurs over a comparatively long period of time; it is not


likely to cause serious damage in a year, for example. We do not normally pro-
vide nozzle or manway liners in new acid tanks, but these can be added to con-
trol corrosion once it is found. Acid tanks should be inspected every 5 years. The
27
inspection should include both a visual and UT examination of the top of man-
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Figure 2.2-A. Hydrogen Grooving at the Top of a Tank Nozzle.

ways and horizontal nozzles for detection of grooving. Additionally, nozzles and
manways can be inspected while the tank is in service by performing on-stream UT.

Not much can be done by way of design to control hydrogen grooving along the
top of horizontal acid tanks. Absorption of moisture from outside air or the acci-
dental entry of rain water can cause rapid tank corrosion. Concentrated sulfuric
acid is hygroscopic; it dilutes itself by pulling any available moisture from the air,
thus creating a corrosive dilute acid. The following measures can help minimize
corrosion:
Design vents to control water ingress.
Devise a method to dry the air pulled into the tank by normal breath-
ing; especially important in hot, humid climates. Tanks that have
been stilled may see corrosion at the vapor/liquid interface where
dilute acids may form.
Use inert gas blanketing.
Take care when cleaning the tank not to allow the formation of
28 dilute acid.
2.2SULFURIC ACID TANKS
ERTC
CONFIDENTIAL

Consider the design and location of inlet and outlet nozzles careful-
ly. Acid velocity through the nozzles should not exceed 3 feet per
second. Do not place the acid inlet nozzle in the top of the tank too
close to the tank wall; grooving of the tank shell could result. Place Underside corrosion of the
the outlet nozzle where it will have good drainage when the tank is tank bottom has more
taken out of service. serious consequences in a
Underside corrosion of the tank bottom has more serious consequences in a sul- sulfuric acid tank than in
furic acid tank than in a conventional hydrocarbon storage tank. When leaking a conventional
acid reacts with moisture in the outside environment, severe corrosion occurs; a hydrocarbon storage tank.
small leak can rapidly become a massive leak. Therefore, it is common industry
practice to build acid tanks on a concrete pad or to support them on I-beams (API
650 Appendix I) to keep the bottom off of the ground. In either case, good
drainage is essential to keep the underside of the tank bottom dry. Larger tanks
built on a conventional sand or compacted soil require careful inspection for
underside corrosion whenever the tank is taken out of service (follow rules of API
653). If a leak is suspected on a flat-bottom tank, a precision volume leak test
may be conducted to ensure tank integrity.

notes

29
2.3FEED COALESCER
ERTC
CONFIDENTIAL

2.3 FEED COALESCER

The feed coalescer removes entrained water from the alkylation plant feed. We
try to limit the amount of water entering the plant to that which is soluble in the
hydrocarbon feed. Water in the feed dilutes the sulfuric acid catalyst. This process If the feed/effluent
results in increased acid consumption because more acid must be withdrawn to exchanger operates
maintain acid concentration within the range where it is both non-corrosive and reliably, coalescer
catalytically active. corrosion is minimal. In
Feed coalescers contain a metal mesh pad, usually stainless steel, upon which the those plants where the
water droplets coalesce and drop to the bottom of the vessel where they are with- coalescer is upstream of
drawn. Shell, heads, and water boot are usually constructed of carbon steel. the feed/effluent
exchangers, corrosion has
We have found that feed coalescer corrosion is also dependent on its location in generally been minimal.
the process. In some plants, the coalescer is located after the feed/effluent heat
exchangers. (A coalescers ability to remove water can be improved with a lower
process temperature.) Depending on the plant, feed/effluent exchangers can have
severe corrosion problems that result in acid-containing reactor effluent being
leaked to the wet plant feed. The wet feed dilutes the acid and results in acceler-
ated corrosion of the plant feed system. Under these conditions, the coalescers

notes
shell experiences accelerated corrosion. In the worst cases seen to date, weld
build-up of the coalescer shell may be required to repair locally thin areas.

If the feed/effluent exchanger operates reliably, coalescer corrosion is minimal.


In those plants where the coalescer is upstream of the feed/effluent exchangers,
corrosion has generally been minimal.

211
2.4STRATCO CONTACTORS
ERTC
CONFIDENTIAL

2.4 STRATCO CONTACTORS

Stratco contactors are horizontal pressure vessels designed to provide intimate


contact between sulfuric acid and the hydrocarbon feed so that the alkylation
reaction can occur. They are normally constructed of carbon steel, but selected
parts are often upgraded to Alloy 20 as corrosion occurs. This corrosion typical-
ly appears in areas of high velocity.

Typical construction of the Stratco contactors is shown in Figures 2.4-A through


2.4-C. A U-tube heat exchanger bundle enters at one end of the horizontal vessel
and serves to keep the reaction mix cool. At the opposite end (the hydraulic head),
an impeller enters. Surrounding the tube bundle is a concentric tube (the circula-
tion tube). The agitator pulls the reaction mix through the circulation tube, over
the tube bundle, and then forces it through the annulus between shell and circu-
lation tube. The goal is to achieve good mixing and temperature control.

A Tube Bundle C Circulation Tube

B Shell D Hydraulic Head

Mix to
Settler
Pressure
Coolant Relief Acid
Out
A B C HC D

Drain Motor
Coolant
In

Figure 2.4-A. Horizontal Alkylation Contactor Assembly

213
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Mix Outlet Vent

Outer Shell Differential


Pressure

Olefin/Refrig. Recycle Feed

Acid Inlet

Saddle Straightening
Circulation Vanes
Tube
Drain

Figure 2.4-B. Contactor Shell Assembly

214
Figure 2.4-C. 63 Hydraulic Head
2.4STRATCO CONTACTORS
ERTC
CONFIDENTIAL

INLET NOZZLES
Every contactor has hydrocarbon feed inlet and acid inlet nozzles or tubes. These
nozzles are generally constructed of Alloy 20 with slots or holes in the end to dis-
tribute and help mix the acid and feed. Burnaby has a distribution ring for their
hydrocarbon feed. Richmond and El Segundo are in the process of upgrading
their feed nozzles to Hastelloy C276. Replacement or repair of the nozzles is usu-
ally necessary every 2-3 years, but nozzles in some plants have lasted 10 years.
The nozzles are either weld repaired, re-ended, or completely replaced. Corrosion
also occurs where the nozzles pass through the internal circulation tube. Alloy 20
collars are often welded to the circulation tube to minimize the corrosion and the
bypassing that causes erosion. Corrosion and leakage of the nozzle between the
OD of the circulation tube and the ID of the shell may permit unmixed weak acid
to flow down to the bundle and cause corrosion.

SPIDER ASSEMBLY
Repairs are often required to this carbon steel vane section. Usually, the leading
edges of the vanes need weld building. The welds that hold the spider assembly

notes
in place are also acid attacked and require repairs. The attachment welds hole
through the circulation tube, causing bypassing and, therefore, accelerated corro-
sion/erosion. Failure of the vanes may lead to severe mechanical damage to the
hydraulic head and impeller. The joint between the spider and the shell circula-
tion tube must be checked for wear or short-circuiting. Additionally, the O-ring
fit between the spider and hydraulic head must be checked for wear to insure a
good seal between the spider housing and the impeller shroud. In general, all
welds should be ground smooth to reduce corrosion potential.

IMPELLER
Most impellers are either Alloy 20 or Ni-Resist. Historically, Alloy 20 has sig-
nificantly lower corrosion/erosion than Ni-Resist. However, since the new Alky
plants were built in Richmond and El Segundo, we have seen several cases of
accelerated corrosion/erosion of Richmond and El Segundo Alloy 20 impellers;
the exact cause of this accelerated corrosion has never been fully understood. In
the mean time, Richmond and El Segundo have installed a few cast Hastelloy C-
276 impellers to see if impeller erosion can be reduced. These Hastelloy
impellers have performed well with no major metal loss.

Impellers with eroded leading edges can be weld repaired. The repair must be
done with care and exactness to maintain the profile of the blade and its critical
dimensions. Unless the casting was made to ASTM 990, there is the possibility
of accelerated corrosion of weld repaired areas. This can be minimized if the
piece is solution annealed after repairs. Objects contacting the impeller while it
is in operation can also cause mechanical damage.
215
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

IMPELLER SHROUD/ WEAR RING


The close-fitting impeller shroud will corrode severely due to localized velocity
increases. Most refineries have modified their shrouds to permit the installation
of a sacrificial Alloy 20 liner on the ID of the shroud. Several methods exist for
its installation, including a welded 3-piece liner, a 1-piece interference fit liner,
and others. Even with the Alloy 20 material, liner weld repairs or replacement are
Keeping a good seal still required. Tolerances between the impeller and shroud affect the mixing of the
between the shroud and acid and hydrocarbon, which can affect corrosion rates. Check the O-ring seating
spider housing is surface for wear. Keeping a good seal between the shroud and spider housing is
essential. essential.

HYDRAULIC HEAD
Check the hydraulic head for corrosion/erosion, paying particular attention to the
vanes within the head. As with the spider assembly, the damage is usually on the
leading or trailing edges. Weld repairs to the head are sometimes necessary and
can be extensive. In several instances, extensive weld repairs have led to general
warpage of the hydraulic head, affecting the important tolerances in the seal area
notes

and other critical surfaces. Be prepared for machine work if weld repairs are more
than cosmetic.

CIRCULATION TUBE AND VANES


Repairs to the circulation tube are infrequent except in the areas where the hydro-
carbon inlet nozzles pass through. Most repairs are to the support vanes and vane
welds. Pay particular attention to the welds that attach to the shell. Shell leaks
have occurred at these attachments. Gauge circulation tube thickness to monitor
corrosion rates. On a few ChevronTexaco contactors, the circulation tube has
been replaced because of thinning.

CONTACTOR SHELL
Most corrosion/erosion problems are in the transition section of the shell. Few
contactor shells need weld repairs; however, in a few instances, corrosion has
been severe enough to require partial or full shell replacement.

CHILLER BUNDLE
In most plants, carbon steel bundle corrosion is generally slow, with bundles last-
ing 10 years or more. However, some plants have severe acid corrosion problems.
In general, most problems are velocity related and cause localized corrosion of
the tubes. Seldom is general corrosion the culprit in tube leakage. Past experience
216
with bundle corrosion has been related to poor acid/hydrocarbon mixing, local-
2.4STRATCO CONTACTORS
ERTC
CONFIDENTIAL

ized high velocities due to bundle design, elevated contactor temperature, and
impingement.

CONTACTOR NOZZLES
External corrosion is likely to be most severe on the contactor nozzles. Inspect
and gauge nozzles for signs of corrosion. Flange faces should be inspected at reg-
ular intervals as well, since weld repairs are common.

CONTACTOR INSULATION
The contactor insulation and weather jacketing should be inspected annually for
the typical problems that can cause external corrosion of the contactor shell.
Follow the guidelines given in Inspection Strategy #19 (External Corrosion -
Corrosion Under Insulation). Pay particular attention to the weather jacketing
joints at the shell nozzles and small-bore piping locations.

notes

217
2.5FEED-EFFLUENT EXCHANGERS
ERTC
CONFIDENTIAL

2.5 FEED-EFFLUENT EXCHANGERS

These exchangers have different names in different plants, but their functions are
similar: they exchange the contactor feed with the acid-containing effluent. The
acid-hydrocarbon effluent (reaction mix) may be on either the shell or tube side.
The efficiency of acid
In all cases, the effluent passes through settler vessels for removal of the gross
removal upstream of the
quantities of acid before entering these exchangers. An Excelso Coalescer may be
exchangers significantly
located ahead of these exchangers. The efficiency of acid removal upstream of
affects the severity of
the exchangers significantly affects the severity of corrosion.
corrosion.
All plants were initially constructed of carbon steel. Tube life varies from 1 to 20
years. Some plants are more corrosive than others, but tube life varies widely
from bundle to bundle, even within a given plant. Tubeside and shellside acid
flow produce different kinds of corrosion, but tube life for both is similar. If the
acid-containing stock is tubeside, the highest corrosion rates occur at the inlet
ends of the tubes because of velocity-assisted corrosion. If the acid-containing
stock is shellside, the worst corrosion appears along the bottom of the shell
because of acid settling. Higher fluid velocities may reduce rather than increase
corrosion in the case of shellside acid flow; the velocity keeps the acid in sus-

notes
pension and prevents it from settling out.

Like other equipment in sulfuric acid service, nozzles tend to corrode more rapid-
ly than the exchanger shell or channel. Flange faces may also corrode. This phe-
nomenon is discussed in the section on piping.

Note that the effluent side of these exchangers contains primarily hydrocarbon,
with a small quantity of acid being entrained as an acid-in-oil emulsion. These are
droplets of concentrated, not dilute, sulfuric acid. In a previous section on sulfu-
ric acid corrosion, we emphasized how important it is to measure acid concen-
trations on an acid-water basis rather than a total basis, when attempting to pre-
dict corrosivity. It is especially important to use this measurement when dealing
with the effluent from the contactor system. This stream is mostly hydrocarbon,
with perhaps only a percent or two of acid downstream of the settlers. However,
the acid in the oil is 96-99% H2SO4, and it is this percentage, not the1-2%, that
the metal faces when contacted by the acid phase.

Despite the frequent short tube life in these exchangers, none has been upgraded
to Alloy 20.

At Pascagoula Alky I, B-7 floating head bolts have cracked, presumably because
of hydrogen stress cracking, an unusual but not unknown phenomenon in alkyla-
tion plants.

These exchangers require frequent repair. The following can be expected in most
plants:
Frequent cleaning on the run because of acid deposits on tubes.
Frequent re-tubing.
Frequent repair or replacement of nozzles. 219
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Weld build-up of corroded flange faces. (Use Alloy 20 if problem is


serious.)
Weld build-up of corroded areas on shell or channel (whichever is
the acid-containing side).
Corrosion rates of carbon steel in these exchangers are affected by the following
factors:
Amount of acid carry-over from the settlers. Upsets cause corrosion.
The amount of acid deposits on the exchanger tubes. Many alky
Keeping the acid deposits
plants bypass these exchangers on the run every year or so for a thor-
under control increases the
ough cleaning and removal of acid deposits. Keeping the acid
life of the exchanger
deposits under control increases the life of the exchanger bundle.
bundle. Process variables
Process variables should be monitored for signs of significant fouling.
should be monitored for
Richmond is unable to by-pass these exchangers, so they have devel-
signs of significant fouling.
oped a method for on-line cleaning. The cleaning will decrease pipe
lifetime, but the benefits are considered worthwhile.
Concentration of acid, as measured on an acid-water basis.
Corrosion rates are lowest at 96-98% H2SO4.
Temperature. Other things being equal, rates should be highest at
notes

the exchanger inlet because the reaction mix is being cooled. Other
factors may mask the temperature effect.
Phase separation.
Opportunity to contact water. See the discussion of flange leaks
and dead legs in the piping section of this manual.
High velocity. We see this effect in exchanger tubes and nozzles.
But velocity is a two-edged sword. We have already discussed the
fact that in some cases a higher velocity may actually be beneficial
by preventing phase separation. Generally, we can say that higher
velocity increases tube and nozzle corrosion but decreases shell or
channel corrosion.

220
2.6ACID SETTLERS AND COALESCERS
ERTC
CONFIDENTIAL

2.6 ACID SETTLERS AND COALESCERS

All alkylation plants have a number of settler vessels, coalescers, and/or precipi-
tators that separate entrained sulfuric acid from the reaction mix. Flow schemes
differ from plant to plant, as do equipment names, but all broadly serve the same
process functionseparation of acid and hydrocarbonand they all have the
same corrosive constituentconcentrated sulfuric acid.

Settlers and coalescers typically have long lives; few have ever been replaced due
Nozzle corrosion, repair,
to corrosion. However, local corrosion does occur, and periodic monitoring usu-
and replacement is
ally finds areas needing repairs.
common. Usually inlet
In a few cases, local external corrosion has been severe. Acid leaks through a nozzles suffer the worst
flange, and because it is hygroscopic, becomes dilute and extremely corrosive as corrosion, but any nozzle
it absorbs water from the atmosphere. Corroding areas are often masked by insu- can be subject to attack.
lation; inspections must be conducted carefully in order to detect corrosion and
correct the cause before damage becomes too severe. Another source of external
corrosion is water accumulation under the insulation. This water can come from
rain or condensation and is usually a result of poor weatherjacketing integrity.

notes
Nozzle corrosion, repair, and replacement is common. Usually inlet nozzles suf-
fer the worst corrosion, but any nozzle can be subject to attack. If not readily
repairable by welding, nozzles are replaced. Replacement nozzles and repaired
nozzles are often protected by an Alloy 20 liner. In some cases, corrosion has
occurred under the liner. Corrosion also appears on bottom drain, sight glass, and
instrument nozzles.

Flange faces often corrode and may leak. They are repaired by weld build-up, and
an Alloy 20 overlay is often used to retard later attack.

Internal corrosion of vessel shells and heads is seldom very severe, but local
repair, after 20 years or more of service, is common. Turbulence around inlet noz-
zles causes local shell attack. In some plants, strip lining of Alloy 20 has been
installed to protect the damaged areas with limited success (strip lining often
leaks). The few attempts to protect the metal with organic coatings have not been
successful. Weld overlay has been the most successful repair technique. On rare
occasions, shells have been butt patched because corrosion became too severe for
weld build-up to be economical.

After 20 years or more of service, acid boots in coalescers and other vessels may
need to be replaced. Selective corrosion of welds is often encountered in con-
centrated sulfuric acid service and has appeared in settlers. On rare occasions,
hydrogen blistering has been reported in shells that have been in service many
years, but the problem has never been severe enough to require vessel replace-
ment or extensive repairs.

Coalescer elements require regular replacement. Alloy 20 and various grades of


stainless steel (Type 304 or 316) have been used. Pad life varies from plant to
plant. Stainless steels reportedly last 1 to 3 years. Alloy 20 appears to last about 221
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

twice as long as stainless steel. Fiberglass pads have also been used; their life
seems to be about equal to that of stainless steel.

Vessel internals, such as supports and distribution headers, are subject to long-
term corrosion and may require eventual repair or replacement. On rare occa-
sions, flange leakage has caused corrosion in manway and flange bolts. These
parts have been upgraded from low alloy to Alloy 20.
notes

222
2.7ACID WASH DRUM
ERTC
CONFIDENTIAL

2.7 ACID WASH DRUM

Some alkylation plants use an acid washer to remove acid esters from the net efflu-
ent stream. Because acid esters have a higher affinity for sulfuric acid than for
hydrocarbon, they can be extracted by mixing a small amount of fresh sulfuric acid
with the net effluent. The sulfuric acid, with absorbed acid esters, is then recycled
to the reaction section, where the acid esters react with isobutane to form alkylate.

Richmond, El Segundo, El Paso, Pascagoula Alky I, and Pascagoula Alky II have


acid wash drums. Generally, fresh acid is injected into the process stream just Because acid esters have
ahead of the acid wash drum and then passed through a static mixer. In the acid a higher affinity for sulfu-
wash drum, the lighter hydrocarbon floats out the top of the vessel; the heavier ric acid than for hydrocar-
acid settles to the bottom. A portion of the separated acid is then re-circulated to bon, they can be extracted
the acid wash injection point; the other portion is sent to the contactors to sup- by mixing a small amount
plement the process catalyst. of fresh sulfuric acid with
the net effluent.
The injection piping, the static mixer, and the piping from the injection location to
the acid wash drum are fabricated of Alloy 20 for corrosion resistance. The settler
is usually fabricated of carbon steel, and general corrosion should be minimal.
However, localized corrosion may be severe at inlet and outlet nozzles and at dead

notes
zones. Some plants have replaced nozzles because of severe corrosion; others have
installed Alloy 20-lined nozzles to control turbulent corrosion. Internal carbon
steel distributors may also corrode from turbulence. In several instances, complete
failure of distributors has led to severe localized shell corrosion.

Acid wash drums employ an electrostatic precipitator to facilitate acid/hydrocar-


bon separation. Precipitator components are subject to corrosion and may need to
be replaced periodically. Corrosion of these components may lead to electrical
shorts when some parts fail completely. Without an operating precipitator,
acid/hydrocarbon separation efficiency is reduced. Consequently, acid carry-over
may occur and may affect downstream alkaline washers by pushing them into an
acidic and highly corrosive condition. The Alky Wars in El Paso during the mid
90s were a result of ESP failure. Similar problems have occurred at El Segundo
and Pascagoula.

For several years, Alky I and Alky II in Pascagoula had severe corrosion of the
precipitator inlet bushing nozzles, top of the vessel, and many precipitator com-
ponents. After several years, it was determined that a purge gas on the bushing
was wet and creating local sulfuric acid corrosion. When the purge gas was dried
or shutdown, the corrosion abated.

Acid leaks can cause weak acids to form on the vessels flange faces, and these
weak acids can cause corrosion. Flange faces are generally weld repaired with
either carbon steel or Alloy 20. The Alloy 20 weld overlay on the flange reduces
corrosion significantly.

223
2.8CAUSTIC WASHERS
ERTC
CONFIDENTIAL

2.8 CAUSTIC WASH DRUMS

Even after passing through settlers and coalescers, the effluent hydrocarbon from
reactors or contactors contains small quantities of entrained sulfuric acid. This
acid must be removed, first by caustic and then by water washing, to avoid acid-
ity in the alkylate product and to prevent corrosion of downstream equipment.

Neither the acid nor the caustic dissolves in the hydrocarbon. Both exist as emul-
sions in the hydrocarbon phase, making caustic washing difficult. When we add
a caustic solution to the reaction mix, we have droplets of both acid and caustic
suspended in the oil. Only by forcing the droplets of caustic to contact droplets
of acidnot an easy taskcan we achieve neutralization. A mixing valve or line
mixer helps us to achieve contacting, but even then, the task is not complete.
Pressure drop across mixing valve or line mixer is an indication of the efficiency
of contacting. The mix valve or line mixer and associated piping from caustic
injection to the caustic settler are often fabricated of Alloy 20. Burnaby and
Hawaii have installed Hastelloy C276 mixing Ts. Even with the metallury
upgrade, leaks have occurred. It is imperative to monitor the mixing Ts for cor-
rosion.

notes
After contacting has occurred, the mixture of hydrocarbon and dilute caustic
enters the caustic settler or caustic wash vessel. The caustic phase settles to the
bottom and is re-circulated. The hydrocarbon phase is withdrawn and sent to the
water-wash system.

In the caustic wash system, dilute caustic is circulating at near-ambient tempera- Running the circulating
tureas non-corrosive a fluid as we could imagine. Even so, considerable corro- caustic to near-neutral
sion occurs in caustic wash systems for two reasons. First, and perhaps most actually causes pH to
important, is the fact that the amount of acid in the caustic wash feed varies from cycle between the acid
time to time. On occasion, gross carry-over of acid is encountered. During these and the alkaline sides.
periods, there may not be enough caustic to neutralize completely; therefore, cor- Combine this fact with the
rosive dilute acids remain. Secondly, plant operators try to minimize the amount inevitable entry of gross
of caustic thrown away with the spent caustic solution that must be withdrawn slugs of carry-over acid,
from the vessel and replaced with fresh. To achieve this economy, they run the and it becomes clear that
circulating caustic to near-neutral, which is fine, as long as the amount of acid we are unlikely to
entering the caustic wash is essentially constant. Unfortunately, it rarely is. maintain non-corrosive
Running the circulating caustic to near-neutral actually causes pH to cycle alkaline conditions.
between the acid and the alkaline sides. Combine this fact with the inevitable
entry of gross slugs of carry-over acid, and it becomes clear that we are unlikely
to maintain non-corrosive alkaline conditions.

Caustic wash drums and settlers are always constructed of carbon steel.
Occasionally they must be replaced because of corrosion, but never in less than
20 years, the normal vessel design life. The exception is the new drum at El
Segundo. After six years of service, the top and bottom heads were replaced.
Corrosion was caused by acid carry-over since the original unit design did not
include an ESP in the acid wash drum.
225
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

The corrosion problems of these vessels are similar to those of acid settlers.
Nozzles often corrode and must be replaced. Where nozzle life is short, some
plants have installed Alloy 20 replacements. Weld metal often corrodes selec-
tively and must be built up. Inlet spargers, where used, have sometimes been
upgraded to Alloy 20, and even these show slow enlargement of the holes. Vessel
shells may corrode selectively around the inlet nozzle because of high turbulence
and acid carry-over.
notes

226
2.9WATER WASHERS
ERTC
CONFIDENTIAL

2.9 WATER WASH DRUMS

Hydrocarbon effluent from the caustic wash contains small amounts of residual
acid or caustic. Although it is generally assumed that this residual is caustic rather
than acid, it is not necessarily so. Corrosion of water wash drums is more severe
and extensive than we would expect from exposure to an alkaline water. In fact,
water wash drums corrode in the same places and at about the same severity as
caustic wash drums. Corrosion varies greatly
Corrosion varies greatly from plant to plant. We assume that this variation reflects from plant to plant. This
the frequency and severity of acid carry-over from the acid settlers. Some exam- variation reflects the
ples are as follows: (The lives given are rounded off for convenience.) frequency and severity of
acid carry-over from the
acid settlers.
Old Richmond The water wash drum suffered local shell corrosion after
20 years because of impingement opposite the inlet
sparger. Some Alloy 20 lining was installed. Severe cor-
rosion of inlet and outlet nozzles occurred.

Old El Segundo The water wash vessel lasted about 40 years before reaching

notes
tmin.

Hawaii The water wash drum has suffered no corrosion. The


Excelso Coalescer just downstream required replace-
ment of the water boot after 30 years.

Pascagoula Alky I The water wash shell has shown little corrosion, but noz-
zles had to be replaced after 20-30 years.

Pascagoula Alky II This plant has an electrostatic precipitator rather than a


simple settling vessel. Major repairs were required to
internals (distributors, grid, and grid supports) after only
3 years. Inlet and outlet nozzles were repaired or
replaced after 6 years. In the coalescer, the water boot
required weld build-up after only 2 years. The bottom of
the vessel and the udder were upgraded to Alloy 20 after
4 years. Inlet and outlet nozzles were lined with Alloy 20
at that time.

El Paso South The water wash drum holed through twice and was
replaced once, all within the first 4 years. Subsequent
corrosion rates decreased, and replacement was next
required after 30 years.

Burnaby The water wash settler and caustic settler are the top and
bottom halves of one piece of equipment. The outlet
nozzle of the water wash passes through the vapor space
of the caustic wash. So, nozzle corrosion is a serious
concern since a leak means introducing water into the
227
caustic. This bottom outlet nozzle leaked three years and
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

eight years after ChevronTexaco acquired the plant. The


second time it leaked, in addition to replacing the nozzle,
a 316L SS liner was installed. The only other corrosion
problem was an inlet nozzle was found holed through
the interior elbow of the distributor. A new distributor
was installed.
notes

228
2.10DEISOBUTANIZER SYSTEM
ERTC
CONFIDENTIAL

2.10 DEISOBUTANIZER SYSTEM

When initially installed, deisobutanizer feed heaters are typically constructed of


carbon steel. They may later require installation of alloy tubes. Corrosion can
occur from the process side, due to entrainment of acid or sludge throughout the
caustic and water wash system. Because these heaters are steam-heated, they are
also subject to attack from CO2 in the steam. Correction of a corrosion problem
requires that the cause of attack be establisheda practice not always followed.
If the heat exchanger has non-stressed relieved welds, caustic carry-over may
cause welds to stress corrosion crack if process conditions are hot enough. The
one known case of alloy upgrading in this service has been from carbon steel to
type 316 tubes after four bundle failures at 6 years average life.

Deisobutanizer columns do not corrode to any significant degree, and attack is


limited to the top of the column. After long service, one plant showed attack of
internal flanges on the reflux line and another showed corroded downcomers on
one tray. Two plants suffered external corrosion under insulation. Some showed
plugging of the reflux distributor and top couple of trays.

Deisobutanizer reflux drums show only nominal corrosion; rates of 3-5 mpy are

notes
typical. The one exception has been Pascagoula Alky I, where the shell was cor-
roded near tmin after 14 years and has since been protected by an internal coating.

DIB overhead condensers show minimal shell corrosion; a rate of 3 mpy is typi-
cal. Tubes are usually admiralty, and process-side corrosion rates are low.
Occasional cases of water-side pitting have been encountered. The biggest prob- The biggest problem with
lem in these exchangers has been the process-side stress corrosion cracking of DIB overhead exchangers
admiralty tubes. This problem has sometimes been attributed to ammonia, as in has been the process-side
one Richmond case, and at other times to sulfates, as in one case at Pascagoula stress corrosion cracking
Alky I and II and another case at Richmond. Figure 2.11-A shows a recent sul- of admiralty tubes.
fate SCC failure from El Pasos DIB overhead.

DIB reboilers are usually all-steel and exhibit very little process-side corrosion.
Tube life is determined almost entirely by steam side CO2 attack. Life can be as
short as 2 years, but 4 or 5 years is more common. Only El Paso North has used
admiralty instead of carbon steel tubes. These tubes are still in service after 30
years.

Corrosion in alkylation distillation systems is caused either by carryover of sulfu-


ric acid from the reactor system or by acidic components (SO2 or SO3) generated
from thermal decomposition of certain acid-hydrocarbon compounds formed in
side reactions in the contactor system. Both types of compounds enter the distilla-
tion system with the contactor effluent stream. Because they have a high boiling
point, they move from column to column, always exiting in the column bottoms.
The sulfuric acid corrodes as it goes. The acid-hydrocarbon reaction products are
not especially corrosive in themselves. However, they thermally decompose to lib-
erate sulfur oxides (SO2 or SO3) when exposed to high temperatures. The decom-
position occurs on the hot wall of reboiler tubes. The acid materials formed there 229
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

corrode the reboiler tubes and go overhead in the column, where they condense
with water, causing attack of overhead condensers, piping, and reflux drums.
Decomposition of these hydrocarbon-based materials is the primary cause of what
little corrosion appears in the distillation train. The amount of these materials
largely controls the severity of corrosion. Reboiler tube wall temperatures deter-
mine where in the distillation train attack occurs. Corrosion appears only when the
metal temperature is high enough to cause thermal decomposition. It can appear
in any one of the columns, but it is most pronounced in the hotter columns.

Figure 2.11-A. Sulfate SCC of an admiralty brass tube from an El Paso DIB overhead condenser

230
2.11BEBUTANIZER SYSTEM
ERTC
CONFIDENTIAL

2.11 DEBUTANIZER SYSTEM

Debutanizer columns have not experienced significant internal corrosion. In one


instance, in Pascagoula Alky I, the column was perforated from external corro-
sion under insulation.

Debutanizer reflux drums have suffered only minimal corrosion. All original
drums remain in service.

Debutanizer overhead condensers are water-cooled. Except for Pascagoula Alky


I, which has steel tubes, all plants use admiralty tubes. The steel tubes at
Pascagoula are still in service after 32 years. About half the original admiralty-
tubed bundles are still in service, the remainder having been retubed once
because of waterside corrosion. Corrosion of the steel shells has been minimal.

Debutanizer reboilers are steam-heated. The reboiler at El Paso North uses admi-
ralty tubes, which have been replaced once due to process-side corrosion. All
other plants have carbon steel tubes. Tubes have been replaced at Richmond
because of process-side corrosion, but all other retubings have been the result of
CO2 attack on the steam side. Tube lives have been as short as a year. A 5-year

notes
life is about average for this service.

231
2.12DEPROPANIZER SYSTEM
ERTC
CONFIDENTIAL

2.12 DEPROPANIZER SYSTEM

The depropanizer has a different location in the alkylation process depending on


plant design. In freon-cooled plants (Pascagoula Alky I and Alky II, El Segundo-
old, and Richmond-old), the depropanizer gets feed from the deisobutanizer over-
head reflux drum. In effluent-cooled plants (El Segundo-new, Richmond-new, El
Paso, Hawaii, and Burnaby), the depropanizer feed comes directly from a reactor
effluent separator (suction trap) via the compressor. Depropanizer corrosion has
generally been the same for the two types of plants, except in the overhead.

FREON-COOLED PLANTS
The older plants (Pascagoula Alky I and Richmond) report heavy fouling of the
upper trays of the depropanizer column. Some replacement of tray parts (chim-
neys and wiers) has been required.

Depropanizer reflux drums have experienced moderate corrosion in some plants


and minimal corrosion in others. At Pascagoula Alky I, the drum was internally
coated twice, after roughly 20 years service. Weld repairs were needed at

notes
Richmond after about 25 years, and again later. A severe upset in 1994 caused
enough corrosion that the vessel required replacement. At El Segundo, the drum
was lined with carbon steel after almost 40 years service and was relined later
with Alloy 20. Corrosion rates at El Paso North have been low.

Shell and tube lives in depropanizer overhead condensers have varied widely
from plant to plant. In several plants, including Pascagoula Alky I and Richmond,
steel shells have been replaced after 20-25 years service. Other plants have shown
minimal shell corrosion. Tube lives have also varied widely. Admiralty was the
tube material of choice in all plants, but in most cases the tubes failed by stress
corrosion cracking after 3 to 20 years. Richmond tried carbon steel tubes but lost
3 bundles in 7 years and is now getting good life from Type 316. Pascagoula Alky
II is now using Saekaphen-coated steel tubes after losing admiralty bundles
twice.

Depropanizer reboilers are constructed of carbon steel in most plants. Steam is


used for heating. Tube failures typically occur as a result of CO2 attack on the
steam side, usually after 15 to 20 years, but occasionally after only 3 years. El
Paso re-tubed with admiralty/steel duplex tubes after losing carbon steel from
CO2 attack. These failed after 15 years due to process-side corrosion of the car-
bon steel.

Depropanizer feed-bottoms exchangers are all-steel and have had long lives. In
the worst case, tube life has approached 30 years.

Depropanizer bottoms coolers are water-cooled and characteristically use admi-


ralty tubes. One admiralty bundle replacement after 20+ years service has been

233
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

reported. Only at El Paso North were steel tubes used in the exchanger; these
failed after 20 years and were replaced with admiralty.

EFFLUENT-COOLED PLANTS
Experience with effluent-cooled plant depropanizers is limited to Hawaii, El
Paso, and Burnaby. The new Richmond and El Segundo plants are also effluent-
cooled, but arent old enough for a history of corrosion.

Corrosion of the depropanizer column has been minimal, with no significant


problems with tray fouling or corrosion.

The El Paso South reflux drum has seen no significant corrosion. Hawaii, on the
other hand, has seen pitting to 150 mils deep and corrosion rates up to 6 mpy.
Hawaii has also had a problem with significant scale accumulation in the drum.

Depropanizer overhead condensers are generally shell and tube type in the older
plants; fin fans are employed in the new plants at Richmond and El Segundo.
Process-side corrosion in El Paso South has been minor, with the majority of cor-
rosion problems from the cooling water. Hawaii has experienced more severe
notes

process-side corrosion with corrosion rates up to 40 mpy on the outlet nozzles.


The outlet nozzle has been replaced and the shell weld repaired.

All other equipment associated with effluent-cooled depropanizers has been


essentially the same as that of freon-cooled depropanizers.

All ChevronTexaco effluent-cooled plants operate with a wet depropanizer. In


this type of system, the depropanizer feed is treated to remove trace SO2typi-
If all SO2 is not removed in cally by caustic washing followed by a coalescer to prevent caustic carryover into
the depropanizer the depropanizer. In some plants, an electrostatic precipitator is used instead of a
pretreatment, the SO2 goes coalescer. The SO2 being removed is from the reaction section of the plant and is
into the depropanizer present in the refrigeration system; it is not corrosive because of the lack of water.
overhead system where it This SO2 must be removed from the propane to meet LPG specification. If all SO2
combines with liquid is not removed in the depropanizer pretreatment, the SO2 goes into the
water to become very depropanizer overhead system where it combines with liquid water to become
corrosive sulfurous acids. very corrosive sulfurous acids. The overhead corrosion problem in Hawaii is
attributable to inadequate removal of the SO2 prior to the wet depropanizer.

234
2.13RERUN SYSTEM
ERTC
CONFIDENTIAL

2.13 RERUN SYSTEM

Rerun stills have not suffered significant corrosion in any of our sulfuric acid
alkylation plants.

Rerun still reflux drums typically corrode at 3-4 mils per year. None have been
replaced to date, nor have any required major repairs due to internal corrosion. In
one plant, external weld repair was needed because of corrosion under insulation.

Rerun reflux condensers typically had admiralty tubes when originally installed.
In most cases, life of admiralty has been good. One plant, Pascagoula Alky I, lost
admiralty tubes after 41 months due to process-side attack. The replacement steel
bundles required replacement 9 times in the next 28 years. At Richmond, one
admiralty bundle failed after 5 years; the cause was not reported. The next one
lasted 20 years. Occasionally, waterside corrosion has caused admiralty to fail
after long-time usage. The steel shells of these exchangers typically suffer little
corrosion, 2-3 mpy corrosion rates being common. At Richmond, the shell and
gasket surfaces have required occasional weld build-up.

Rerun still reboilers are carbon steel in all plants. Corrosion rates have been very

notes
low. Worst-case tube life is on the order of 25 years.

Alkylate coolers at Pascagoula Alky II were originally carbon steel, but the first
two bundles lasted 1 and 2 years respectively. They were upgraded to Type 316,
damage to the carbon steel having been attributed to acid attack. Other plants
generally have admiralty tubes, which have shown long lives.

235
2.14SPENT ACID WEATHERING DRUMS
ERTC
CONFIDENTIAL

2.14 SPENT ACID WEATHERING DRUMS

Spent acid weathering drums are always built of carbon steel. They handle spent,
concentrated sulfuric acid, characteristically suffer from localized corrosion, and
require extensive maintenance. In some cases, Alloy 20 is used for partial shell
linings or for nozzle protection. The following case histories provide an idea of Spent acid weathering
what to expect in this service: drums handle spent, con-
centrated sulfuric acid.
Burnaby Two years after ChevronTexaco started operating this
They characteristically
plant, the Relief Knock-Out Drum, as it is called there,
suffer from localized cor-
had to be replaced. Steam had been introduced into the
rosion, and require exten-
vessel in order to accelerate the weathering process. As
sive maintenance.
a result, the vessel corroded enough to need replace-
ment. The new vessel shows a tideline with pitting
below the line 0.06-0.09" deep.

El Paso North Inlet nozzles were replaced and tray holes patched after
11 years. The shell locally corroded to tmin after 16 years
and was lined with Alloy 20 in the corroded area. Several
butt patches were required in the shell in later years.

notes
Hawaii The original weathering drum required replacement after
15 years service. The shell had suffered extensive corro-
sion at the operating acid surge level, and partial lining
with Alloy 20 resulted in corrosion of the lining welds.
The carbon steel replacement vessel lasted only 11 years,
despite regular changes in acid level to move the zone of
worst attack. The third vessel in this service required
replacement of the bottom nozzle after 2 years and exten-
sive weld build-up of the shell after 5 years. Corrosion
rates are said to average 50 mils per year. A Teflon liner
was installed in the bottom outlet nozzle. It leaked after
six years and was replaced in kind. At that time, the ves-
sel interior was coated to prevent further corrosion.

Pascagoula Alky I The original drum lasted only 8 years, despite attempts
to control corrosion by applying alloy 20 strip lining.
The replacement vessel had a 12 band of Alloy 20
cladding. This vessel leaked after 11 years due to corro-
sion just above the cladding. As a result, part of the shell
was replaced. On several subsequent occasions, it was
necessary to apply some Alloy 20 strip lining.

Pascagoula Alky II The original vessel had been clad with Alloy 20, and the
bottom head was strip lined as a precaution after 3 years
service. The spent acid inlet nozzle was replaced with
Alloy 20 after 1 year of service. Six years after start-up,
it was necessary to make weld repairs to the shell. 237
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

Richmond Corrosion has been relatively mild. Rates have not


exceeded 10 mpy.

El Segundo The weathering drum has required only minimal atten-


tion. The bottom nozzle was replaced, but only after
many years of service. Occasional weld repairs to the
bottom head were required over the years.
notes

238
2.15MISCELLANEOUS EQUIPMENT
ERTC
CONFIDENTIAL

2.15 MISCELLANEOUS EQUIPMENT

CAUSTIC DEGASSERS
Caustic degassers suffer from a surprising amount of corrosion for what ought to
be a non-corrosive service. At El Paso North, a butt patch was installed after 11
years service, numerous weld repairs having previously been made. The vessel
was replaced at the age of 17 years. The replacement vessel lasted only 2 years.
The next vessel to be installed had the lower third lined with alloy 20. The cor-
rosion, it is believed, was caused by foaming and acid carry-over from the spent
acid weathering drum.

At Pascagoula Alky I, several nozzles had to be replaced before a new vessel was
installed after 18 years. After another 4 years, this vessel was again replaced, this
time with an Alloy 20 drum. The Alloy 20 has shown little corrosion.

Corrosion of caustic degassers can be directly attributed to acid carryover from


upstream equipment that overwhelms the finite volume of caustic in the degasser
system. This acid upset creates hot and weak sulfuric acid which aggressively

notes
corrodes equipment.

RELIEF DRUMS
Carbon steel relief drums have shown a variety of problems, varying in severity
from plant to plant. Shell corrosion has sometimes been severe, requiring period-
Shell corrosion of relief
ic weld build-up. Shells have corroded to tmin in as short a time as 10 years,
drums has sometimes
requiring partial replacement strip lining. Steam coils have corroded to failure in
been severe, requiring
as short a time as 3 years and have sometimes failed by caustic stress corrosion
periodic weld build-up.
cracking. In at least one plant, the vessel shell has suffered caustic SCC repeat-
edly, adjacent to the point of heating coil entry. In one instance, the heating coil
has been upgraded to Alloy 20. Nozzles in the vessel have also required frequent
repair or replacement. One identified cause of corrosion has been acid carryover
into the relief drum from various locations in the plant.

Some plants have dedicated relief systems and associated relief drums for acid
services versus non-acid services. Because potentially water-carrying processes
are routed to another relief system, plants with a dedicated acid relief system
should experience less relief system corrosion.

PUMPS
Fresh acid or acid recirculating pumps of carbon steel have shown lives as short
as one month. Alloy 20 is the current standard for this service. Carbon steel
pumps handling reactor or contactor effluent have generally shown adequate life.
When attack occurs, it is often due to acid collecting at the bottom of the case 239
SENIOR ANALYST AND INSPECTOR TRAININGH2SO4 ALKYLATION

when the pumps are idle. Caustic washer recirculation pumps of carbon steel
have shown lives of 2 to 15 years, rate of corrosion largely depending on the
amount of acid carryover into the caustic wash system. Experience with water
washer recirculation pumps is generally similar. In both cases, Alloy 20 is being
used where better materials are required.
notes

240
Senior Analyst and Inspector Training,
H2SO4 ALKYLATION
1. Process Overview
2. Acid Strength Discussion
3. Corrosion of Carbon Steel by H2SO4
4. Hydrogen Damage of Steel by H2SO4
5. Corrosion of Stainless Steels by H2SO4
6. Alloy 20 in H2SO4
7. Purchasing Requirements for Alloy 20 Castings
8. Welding Alloy 20 Cb-3
9. Nickel-Based Alloys in H2SO4
10. Other Metals in H2SO4
11. Summary of Metallic Materials for H2SO4 Service
12. Nonmetallics in H2SO4
13. Corrosion Under Insulation/Some Things to Remember
14. Brittle Fracture
15. Caustic Cracking and Corrosion
Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
Materials and Equipment Technology Unit permission of ERTC 1
04/03/02 mrb Sec3-1-G020306 Niccols
1. Process Overview

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
ChevronTexaco 2001 Materials and Equipment Technology Unit permission of ERTC 2
04/03/02 mrb Sec3-1-G020306 Niccols
Sulfuric Acid Alkylation
Process Introduction
for Senior Analysts and Inspectors

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
ChevronTexaco 2001 Materials and Equipment Technology Unit permission of ERTC 3
04/03/02 mrb Sec3-1-G020306 Niccols
Sulfuric Acid Alkylation Process Introduction

Safety Topic Motiva Delaware Spent Acid Tank Fire


Alkylation General
Effluent Refrigeration Alky PFD
Closed Cycle Refrigeration Alky PFD (Pascagoula)
Reaction Chemistry
Operating Conditions
Contaminants in Feed
Process Details Critical Reliability Variables
General Depropanizer
Reaction Section Acid Wash/Alkaline Water Wash
Refrigeration Section (Effluent) Spent Acid Degassing/Blowdown
Refrigeration Section (Closed Cycle)
Corrosion Issues Alky Unit Inspection Guideline Best Practice
Effect on Corrosion/Reliability due to
High Olefin Feed Rates Water
C3/C5 Olefin Processing Section Temperature
Acid Runaway Prevention Best Practice
Question and Answer Session Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
Materials and Equipment Technology Unit permission of ERTC 4
04/03/02 mrb Sec3-1-G020306 Niccols
Alkylation General

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
ChevronTexaco 2001 Materials and Equipment Technology Unit permission of ERTC 5
04/03/02 mrb Sec3-1-G020306 Niccols
Refining Map
Refinery General Process Flow
Gasoline C1-C4
Stabilizer/
Splitter LSR Gasoline

No. 1 Side Cut


Jet
No. 2 Side Cut Merox
No. 3 Side Cut Diesel

nC4 Isomerization iC4


C3
Crude Distillation Unit

Unit
H2 N-Butane
Hydrogen
Crude MFG.
C4 & Lighter
Lt Alkylate
Gas Oil Alky
Hydrocracker iC4 Unit Alkylate
C3 Olefins Polymer
Poly
MTBE
C4 Olefins
~
MTBE ~
Gas Oil FCC Unit C5 Olefins FCC Gasoline
TAME Caustic
Treating TAME
~

~
Light Cycle Oil
Heavy Cycle Oil & Bottoms

Olefins
Coker Gasoline
Coker
Coker Gas Oil
Asphalt
Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
Materials and Equipment Technology Unit permission of ERTC 6
04/03/02 mrb Sec3-1-G020306 Niccols
Purpose of Alkylation
Upgrade Low Value Olefins
Component BP, F RVP, psia
C3 = -54 220
C4 = 33-38 50-60
C5 = 70-90 20-25
iC4 11 70
BP = Boiling Point RVP = Reid Vapor Pressure

Olefins Alkylates
RON MON RON MON
C3= 100 85 89-91 88-90
C4= 94-100 80-83 94-98 92-94
C5= 90-100 80-85 90-92 88-99
RON = Research Octane Number MON = Motor Octane Number
z Produce Clean Component for RFG
No Olefins or Aromatics
Low RVP and High Octane
Dilution Effect, Very Low Sulfur
See RFG Specs
z Produce Product Propane and n-Butane
z Typical Alkylate Specifications From Combined C3=/C4=/C5= Feed
RVP, psia T50, F T90, F EP, F RON MON
7.0 211 261 385 92-94 90-92
Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
Materials and Equipment Technology Unit permission of ERTC 7
04/03/02 mrb Sec3-1-G020306 Niccols
Clean Burning Gasoline (CA) and
Federal RFG Specs
Federal RFG CBG2 CBG3**** CBG2 CBG3

Typical Flat Limits Flat Limits Caps Caps


RVP, psi
6.8 7.0 7/6.9* 7.0 6.4-7.2
(Summer)
Aromatics, Vol % <30 25 25 30 35

Olefins, Vol % <12 6 6 10 10

T90, F 310-330 300 305 330 330

T50, F 190-220 210 213 220 220

Oxygen, Wt % 2.0 min 1.8-2.2 1.8-2.2 1.8-2.7 0-3.7**

Sulfur, ppm <120 40 20 80 60/30***

Benzene, Vol % 1.0 max 1.0 0.80 1.20 1.10

* Flat limit is 6.90 if using the evaporative model.


** Up to 3.7 wt %, but not more than 10 Vol % ethanol; MTBE ban effective Jan 1, 2004 in California.
*** Cap reduced to 30 ppm effective 12/31/04.
**** CBG3 specs effective January 1, 2003 based on predictive model.
Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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Where Are Chevron North America
Alky Plants?

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
To be reproduced and used only in accordance with written
Materials and Equipment Technology Unit permission of ERTC 9
04/03/02 mrb Sec3-1-G020306 Niccols
The Chevron Alkylation Plants in
North America

Alkylate, # of # of Acid
Chevron Plant MBPD Contactors Stages
Hawaii, Effluent Refrigeration 5 3 3
El Paso, Effluent Refrigeration 8 3 3
Burnaby, Effluent Refrigeration 4 2 1
Pascagoula Alky I, 134a Refrigeration 10 6 5
Pascagoula Alky II, 134a Refrigeration 11 4 3
Richmond, Effluent Refrigeration 25 12 3
El Segundo, Effluent Refrigeration 25 10 3
Salt Lake, UOP HF Acid 5 N/A N/A
Total 93 40

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Energy Research and Technology Company
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Sulfuric Acid Alkylation
Future
Alkylate is 15-20 Vol % of California RFG Gasoline Pool on the
West Coast Post 1996 (CBG 2) Versus 8 Vol % pre-1996
Alkylate is Prime Component for California RFG
No Olefins and Aromatics (100% Paraffinic)
Low RVP and High Octane
Dilution Effect
In Fact, the Entire California Reformulated Gasoline Pool Would
Ride on Ability to Make Alkylate in Large Quantity Less
Critical Outside California But Still Important
Other States Adopting CARB II Regs in 2004
CNAP Commissioned Two New 25 MBPD Alkylation Plants at
Richmond and El Segundo (1st Quarter 1996) Includes
C3/C4/C5 Olefin Alkylation

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Effluent Refrigerated
H2SO4 Alkylation Unit
Refrigeration Section Distillation Section

Reaction Section

Feed Section

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G9600300 Copyright 2002 by ChevronTexaco
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Pascagoula Alkylation Plant
Freon Refrigeration Section

Confidential
G9600981 Copyright 2002 by ChevronTexaco
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Reaction Chemistry

Confidential
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Energy Research and Technology Company
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How Overall Alkylation Works

Olefins Sulfonic Acid/


Water SO2 Polymers

Step 1 Step 2 Step 3 Step 4 Alkylate

Acid Esters
Isobutane

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Alkylation Chemistry
(Desirable Reaction Summary)
Direct Alkylation of Isobutane With Olefins to Product C7 to C9 Isoparaffins
Steps 1, 2 and 3
Olefin + Sulfuric Acid Monoalkyl Sulfate (Intermediate Acid Ester)

C4H8 + H2SO4 (C4H9) HSO4


Step 4
Isobutane + Monoalkyl Sulfate Isoparaffin + Sulfuric Acid

C4H10 + (C4H9) HSO4 TMP + H2SO4

Reaction Pathway Summary and Volume Balance


Exothermic
1.0 Bbl Butene + 1.13 Bbl Isobutane 1.74 Bbl Alkylate
+ 615 Btu/Lb Butene Alkylated

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Alkylation Chemistry
(Undesirable Side Reactions)

Step 1 - Sulfonic Acid Production


Olefin + Sulfuric Acid Sulfonic Acid + Water
C4H8 + H2SO4 C4H8SO3 + H2O

Step 2 - SO2 Production


Olefin + Olefin Conjunct Polymer + Heat
Conjunct Polymer + Sulfuric Acid Reactive Olefin + Sulfur Dioxide + Water
C8H16 + H2SO4 2 C4H7 + + SO2 + 2 H2O

Step 2 - Ester Production


Olefin + Acid Ester Neutral Ester
C4H8 + (C4H9) HSO4 (C4H9)2 SO4

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Alkylation Chemistry
(Undesirable Side Reactions)

Step 4 Side Reaction


Polymerization Type C4= + iC4+ TMP+ (Trimethylpentane)
Reactions That TMP+ + 2C4= C16+
Fragment to Produce
C16+ C7+ + C9+ + H- C7 + C9
C5 to C10 Isoparaffins

Step 4 Side Reaction


Polymerization Type C4= + iC4+ TMP+
Reactions That Do Not TMP+ + C4= C12+
Fragment to Produce
C10+ Isoparaffins C12+ + H- C12

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Alkylation Chemistry
(Undesirable Side Reactions)
Step 4 Side Reaction
Production of Isopentane and Trimethylpentanes
When Alkylating Amylenes (Also Production of
Propane When Alkylating Propylene)

nC5= + iC4 TMH+


TMH+ iC5= + iC4+ iC5 + iC4=
C4= + iC4 TMP
Overall, nC5= + 2iC4 iC5 + TMP

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Alkylation Reactions General

Reactions Take Place in Acid Continuous, Liquid Emulsion Phase


Emulsion Provides Surface Area for Reaction = Good Mixing
Alkylation is Favored by Lower Temperatures
Need Lots of Isobutane in the Reaction Zone

Esters are Intermediate Compounds Some Esters Will Be Produced Even at


Ideal Reaction Conditions
Acid Strength Influences Reaction Pathway (Desirable and Side Reactions)

Hydrocarbon Continuous Emulsion Results in More Polymerization Reactions


Higher Temperatures Result in More Side Reactions
Lack of Isobutane in Reaction Zone Results in More Side Reactions

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Optimum Operating Conditions for
Sulfuric Alkylation

Variable Optimum Typical


Isobutane Concentration in
Reactor Effluent, LV % 62-70 55-75
Olefin Space Velocity, 1/Hr 0.2-0.3 0.3-0.5
Reaction Zone Temperature, F 45-50 42-65
Acid in Contactor, LV % 50-60 40-60
Spent Acid Strength, Wt % 88-92* 88.5-91.5

*Function of olefin feed type

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Feed Contaminants

Contaminant Where it Comes From What it Does How To Control it Typical, ppmw
Water Numerous Upstream Consumes Acid; Adds to Regular Draining of Olefin 100-200
Sources Corrosion Feed and Iso Recycle
Coalescers and Sensidyne
Tube Water Measurement
Methanol/ MTBE/TAME Units Increase Acid Control at MTBE/TAME Plant Methanol-50
Consumption and
DME DME 1000-2000
Corrosion
Mercaptans/ Dependent on Feed Consumes Acid; Makes Check Upstream Operations 30-250
Quality To FCC ASO (Acid Soluble Oil)
Disulfides
Ethylene FCC Gas Recovery Unit Does Not Alkylate, But Check With FCC 0
Forms Stable Esters -
Increased Acid
Consumption
Dienes Function of FCC Higher EP Alkylate (5F) Install Selective 2000-6000
Reactor Temperature High Acid Consumption Hydrogenation Unit
and ZSM-5 Catalyst (SHU) ZSM-5 Lowers
Dienes Make
Aromatics Gasoline That is Used Causes Severe Foaming in Have Stored Alkylate on 0
For Startup When Effluent Treating Section Hand For Startup
Alkylate is Not
Available

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Process Details

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Reaction Section
STRATCO Contactor Reactor

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Contactor Reactor/Acid Settler
Arrangement

Acid Settlers
Spent Acid
10 Dia.
1700 gpm
2000 gpm Fresh Acid
To Suction Trap/
Flash Drum 12 Dia.

PC
500 hp M Contactors

Refrigerant Recycle

50,000 gpm
Internal Circulation
Olefin Feed
and Recycle ISOBUTANE Confidential
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Refrigeration System With Total
Condenser and Economizer

Confidential
G9600301 Copyright 2002 by ChevronTexaco
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Freon (Now 134a) Refrigeration
Pascagoula Alky II

Confidential
G9601102 Copyright 2002 by ChevronTexaco
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Depropanizer Feed Treating

Depropanizer
Feed
Propane
Product
D Treated Water
E
P
R
O
P
A Caustic
N Coalescer
Wash
I
Z
E
R

To Flash Spent Fresh


Drum Caustic Caustic

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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Net Effluent Treating

Net Effluent to
Net Effluent
DIB

Fresh Acid

Alkaline
E.P. Acid
Water Wash
Wash
Fresh Acid to Alkylate
Contactors Product

Hot Alkylate
Product

Makeup Acid Circ. Spent Alkaline


Water Pump Water

Caustic From
Caustic Wash Drum

Alkaline Water
Circulation Pump

Confidential
Copyright 2002 by ChevronTexaco
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Electrostatic Precipitator

Bushing Housing Energized


Bushing
Outlet Inlet
Housing

Energized Hanger
Rod

Enclosure
Flow

The electrostatic precipitator coalesces droplets of an electrically conductive


phase (acid) dispersed in an non-conductive phase (hydrocarbon). A high
voltage, direct current, electrostatic field is used to achieve the separation. The
field is highly non-uniform, which causes rapid random motion of conductive
acid droplets. This promotes many collisions and subsequent coalescence of
acid droplets.
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Spent Acid
Acid is Spent in Three Ways:
Dilution With Water/Contaminants
Dilution With Desirable Side Reactions
Dilution With Undesirable Side Reactions
(Excessive Ester, Polymer, and ASO)
Consists of Acid, Acid-Soluble Oil and Water
Gravity of Acid ~1.8
Gravity of ASO ~0.8
Gravity of Water ~1.0
Simple Measurement of Gravity by Coriolis Meter Can be Correlated
to Give Acid Strength; But Needs Model Development for Particular
Feed Type
Good Alkylation Conditions Result in:
1-2 Wt % Water in Spent Acid
7-9 Wt % ASO in Spent Acid
Higher Water Content and Lower ASO at Same Acid Concentration
Makes Poorer Octane
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Cascaded H2SO4 Flow

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G020286 Copyright 2002 by ChevronTexaco
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Acid Degassing
Typical
Spent Acid From To Flare
Reaction Section
Caustic
Acidic Blowdown Vapor
Streams Scrubber

Fresh
Caustic
Acid Degasser

Spent
Acid to
Storage

HC to Caustic to
Reaction Section Caustic Wash Drum

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5.1 Corrosion Issues General

General Corrosion of CS is Usually Not a Problem


at Design Acid Strengths and Process Conditions Used in
Alkylation
Keys to Minimize Corrosion/Fouling
Good Reaction Conditions (Temp., Olefin Rate, I/O )
Low Velocity and Temperature in Acid Lines
Dont Let Alkylation Acid Sit Stagnant
Minimize Contaminants in Feed (Water, Etc.)
Keep Acidic Streams Dry and Wet Streams Neutral
Operate Treating Section Within Recommended Guidelines
Process Monitoring for Corrosion Control Best Practice
Stay Alert in Units Pushed Above 0.5 OSV Especially With C3=

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Localized Corrosion of Carbon Steel in
Acid Service
In Piping, if Velocity >3 Ft/Sec. (Rec: 0.7 Ft/Sec.)
In Valves, Because of Turbulence
(Use Alloy 20 Valves)
At Hot Spots Caused by Heat Tracing
Use Long Radius Alloy 20 Elbows With One Feet Pup
of Alloy 20 at Each End
Experience Shows Corrosion Concentrated at Top of
Pipe (Long Runs From Tankage Can Rotate 180
Over Time)
Refer to Alky Unit Inspection Guideline Best Practice

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Corrosion of Steel by
Sulfuric Acid
0.15
0.14 Corrosion of Steel by 150F
Sulfuric Acid Temp. Flange Quality Specifications
0.13 80-150F Carbon 0.25 % Max.
120F
0.12 Manganese 0.30-0.60%
Phosphorus 0.05% Max.
0.11 Sulfur 0.05% Max.
Inches Penetration Per Year

Steel Completely Immersed


0.10 Acid Not Stirred
0.09 Loss as Inches
Penetration/Year
0.08 100F
0.07
0.06
0.05
0.04 80F 150
120F F
0.03 120
F
0.02 80F 100
100F F
0.01 80F
0
50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66
Baum

62 64 68 72 76 80 84 88 92 94 96 98 100
Confidential
H2SO4, % Copyright 2002 by ChevronTexaco
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Reaction Section Fouling/Corrosion

Feed/Effluent Exchanger Corrosion Due to Weak


Acid Fouling Due to Ester Breakdown in the Tubes
Spent Acid is Reactive and Can Solidify if Left
Stagnant
Flush Sight Glasses and Level Instruments Weekly
Drain Spent Acid From Stagnant Lines
Fiberglass Elements in Feed Coalescers Break Down
if pH is Outside 5-9 Range (El Segundo, Pascagoula
Alky I, El Paso)
Contactor Tube Bundle Fouling is Usually Caused by
Acid Carryover and Seen in High Strength Contactors
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Reaction Section Corrosion

Minimizing Water and Contaminants (Methanol )


in the Feed Saves Acid and Reduces Corrosion
Localized Corrosion Can Occur Where Wet and
Acidic Streams Are Mixed in Areas of High Velocity
Use Alloy 20 Where Corrosion Potential is High
Wet Flush to Contactor Seals Causes Severe Shaft
Corrosion

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Corrosion and Fouling

Component Review Diagram

Fouling Constituents/Mechanisms

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Alloy Contactor Components

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G9600986 Copyright 2002 by ChevronTexaco
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Effluent Refrigeration Section Corrosion

SO2 From the Reaction Section Accumulates in the


Refrigeration Section
The Refrigeration System Should Be Dry
Any Water Present Will Accumulate in the
Depropanizer Overhead
The Combination of SO2 and Water (From
Depropanizer Feed Caustic Treating) Corrodes
Carbon Steel
Depropanizer Overhead Water pH Provides
Indication of Treating Performance

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Corrosion in Closed Loop Refrigeration
(Freon 134a)
If No Leak in Contactor, No Major Corrosion Issues
However, Contactor Tube Leaks Are Fairly Common
and Result in >$1.0 MM Per Incident Cleanup Cost of
134a System
Pascagoula Now Replaces Contactor Bundles on
Preventative Basis Before a Leak Can Occur

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Depropanizer System
(Effluent Refrigeration)
Good Feed Treatment Operation Insures Minimum
Corrosion
Poor Feed Treatment Increases Corrosion Because it
Provides a Source of Water

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Depropanizer Feed Treatment

DEC3 4 DEC3
Mixer
Feed Feed

Alloy 4
20
Caustic
Coalescer
Wash
Degas.
Drum
Caustic
To AWW

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Depropanizer Caustic
Wash Operation
In Effluent Refrigerated Units, SO2 and Entrained Acid Are
Neutralized in Depropanizer Feed to Prevent Corrosion
SO2 + NaOH NaHSO3
SO2 + 2NaOH NaSO3 + H2O
5-Element Static Mixer Typical P 7-15 psi,
Droplet Size 300-400 Micron
Caustic Circulation 20-30% of the Depropanizer Feed by Volume
Batch System Guidelines
Minimum Spent Caustic Strength 3 Wt %
Add Fresh Water to Make Up for Losses to the Hydrocarbon Stream
Measure Caustic Strength in Addition to Caustic Specific
Gravity Caustic Strength Preferred <10 Wt %
Overhead Accumulator Water pH Should Be 6-7
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Acid Wash/Alkaline Water Wash
(Except Hawaii)

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G020288 Copyright 2002 by ChevronTexaco
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Treating Section

Purpose is to Prevent Corrosion and Fouling in


the Fractionation Section
The Net Effluent Treatment System Removes
Free Acid
Monoalkyl Sulfates (Acid Esters)
Dialkyl Sulfates (Neutral Esters)
All Chevron Alky Plants Have Acid Wash/Alkaline
Water Wash System Hawaii Has Chosen to Use
Caustic/Water Wash System, Bypassing the Acid
Wash

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Net Effluent Acid Wash Operation

Acid Extracts Acid Esters and Recycles Esters Back


to Reactor Section
5-Element Static Mixer Typical DP 5-10 psi, Droplet
Size 300-400 Micron
Acid Circulation Rate 3-5% of DIB Feed by Volume
Electrostatic Precipitator (ESP) Prevents Acid
Carryover (<10 ppm Acid in Net Effluent)
Maintain Flow of Dry Bushing Flush to ESP Insulators
Monitor Voltage and Amperage

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Alkaline Water Wash Operation

Alkaline Wash Breaks Down Neutral Esters at 120F and


Neutralizes Any Acid Carryover
5-Element Static Mixer Typical DP 7-15 psi, Droplet Size
300-400 Micron
Water Circulation Rate 20-30% of DIB Feed
Bulk Alkaline Wash Drum Temperature 120F
Add Caustic to Maintain pH 10-12; Ensure pH Analyzer is Well
Maintained
Adjust Make-Up Water to Maintain TDS <8000 Mmhos/cm
Makeup Water Should Be Treated Water
DIB O/H Water pH is Indicator of Treating Performance
Analyze Acid Content in Net Effluent to DIB if Performance of
ESP is Suspect
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At Temperature 120F Dialkyl
Sulfates React (Alkaline Water Wash)

Saponification
(C4H9)2SO4 + NaOH NaSO4(C4H9) + C4H9OH

Hydrolysis (Main Reaction)


(C4H9)2SO4 + 2H2O 120F 2C4H9OH + H2SO4
(Neutral Ester)

Neutralization
H2SO4 + 2NaOH Na2SO4 + 2H2O

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Chevron El Paso Refinery
DIB Overhead Water Analysis

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Caustic Wash/Water Wash
(Hawaii and Burnaby)
Net Effl. Mixer Mixer DIB Feed

Caustic Wash Water Wash

Blowdown

NaOH
Blowdown
H2O

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Typical Net Effluent Caustic
Wash Reactions (Hawaii and Burnaby)
Saponification
(C4H9)HSO4 + NaOH NaSO4(C4H9) + H2O
(Acid Ester)

Hydrolysis
(C4H9)HSO4 + H2O C4H9OH + H2SO4
(Acid Ester)

Neutralization
H2SO4 + 2NaOH Na2SO4 + 2H2O
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Other Corrosion/Problem Areas

ESP Bushing Housing Corrosion Due to Wet Flush


Fouling of Alkaline Water Exchangers Due to Hard
Water (Preferably Need Soft Deaerated Water)
Low Caustic Strength in Acid Gas Caustic Scrubber
(High Strength Leads to Pluggage; Very Low
Strength Can Be Overwhelmed With Acidic Gases)
Corrosion in Alkaline Wash Mixer Bypass

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Alkylation Unit Relief Systems

Two Relief Systems in Alkylation Units


Acid Relief System (Dry, Acidic Vents)
Reaction Section
Refrigeration Section
Acid Wash
Acid Blowdown Drum
Relief System Corrosion is Prevented by Keeping Acidic Vents Dry

Refinery Flare System (Wet, Nonacidic Vents)


Caustic and Water Washes
Depropanizer
Fractionation Section
Corrosion is Prevented by Keeping Nonacidic Vents Neutral

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Blowdown Section

Refinery Flare
Acid Relief
Blowdown
Vapor
Spent Acid Scrubber

Acid Blowdown Alloy Fresh NaOH


Drum 20

Blowdown

Spent
Acid

HC
Recycle

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Energy Research and Technology Company
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Effect on Reliability/Corrosion Due to
High Olefin Rates
Higher Contactor Temperature
Higher Acid Consumption
Lower Iso/Olefin Ratio/Lower Alkylate Octane
More Side Reactions
Increased Acid Carryover Potential
Inadequate Treating Possibility
Less Room for Error (Example: El Paso OSV = 0.5 Versus
Hawaii = 0.25; New Design = 0.3) ESP Performance is Critical
DIB, Debutanizer Corrosion/Fouling if Inadequate Treating
Increased Maintenance Costs

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Effect on Reliability/Corrosion Due
to Propylene/Amylene Processing
Propylene Consumes More Acid Than Butylene and
Amylene
Probability of Contaminants is Increased
(C6+, Oxygenates )
Propyl Esters Are More Difficult to Treat
If High Amounts of Propylene in Total Olefin Feed
(>80%), Acid Runaway Probability Increases
Less Room for Error (Acid Strength Measurement,
Inadequate Mixing, Etc.)
ESP Performance is Critical to Prevent Acid
Carryover
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Effect on Reliability/Corrosion Due to
Water
Sources of Water:
Feeds and Isobutane Recycle
Fresh Acid
Alkaline Water and Caustic Wash
Steam Reboiler Leaks
Reaction By-Product
MeOH, DME and Ethers From MTBE and TAME Units
Poor Reaction Conditions

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Effect on Reliability/Corrosion Due to
Temperature
Typical Temperature Profile
Steam Reboiler Leaks
Reaction By-Product
MeOH, DME and Ethers From MTBE and TAME Units
Poor Reaction Conditions

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Copyright 2002 by ChevronTexaco
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Acid Runaway

Acid Runaway Fundamentals


Acid Runaway Recognition
Acid Runaway Response
Possible Causes for Acid Runaway
Handling of Runaway Acid

Acid Runaway Prevention Best Practice

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Reactions

Desired Reaction
Olefins + Isobutane Alkylate + Heat
Olefin Btu/Lb
C3= 840
C4= 615
C5= 500

Undesired Reactions
Olefin + Olefin Conjunct Polymer + Heat

Conjunct Polymers + H2SO4 SO2 + H2O

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Acid Runaway Fundamentals

Acid Runaway Starts to Occur Below 85 Wt %


Polymerization is Favored Over Alkylation
Polymers Are Highly Unsaturated and Soluble in Acid
At Some Point Acid Addition Cannot Keep Up and
Drops Further Polymerization Can Only Stop if
Olefin is Cut Off
Heat of Reaction of Polymerization is Less Than
Alkylation, so Temperature Goes Lower
Oxidation of Polymers by H2SO4 Also Starts
Producing Tar, SO2, and Color Bodies
Density of Acid Phase is Reduced and Separation
Becomes Difficult
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Acid Runaway Recognition

Online Reliable Continuous Acid Analyzer Can Prevent Incidents


Key is Drop in Temperature in Lowest Concentration Contactor Temperature
Drop of Up to 18F Has Been Seen (at Constant Olefin and Refrigerant Rates)
Another Indication is Lower DP Across Impeller and Lower Amps
Settler and Contactor Ratio Glass Should Be Checked if There is Suspicion
(Resolve Time, Acid/HC Ratio, Acid in Higher Split Glasses)
Increased SO2 in Depropanizer Feed; Fast Caustic Depletion Also Wash
Water pH Goes Low
Purple/Reddish Alkylate (High EP, Lower Yield)
DIB and Debutanizer Start Losing Heat Transfer
Wild Acid Heat Up Test
Spent Acid Sample Analysis Every Half Hour Pull Sample Directly From
Contactor if Possible
Sometimes All of Above Are Not Seen at Same Time Due to Large
Hydrocarbon Residence Time

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Contactor Amperage
Runaway Profiles

40

30
Amperage

A Amperage

25
B Amperage

20
0 1 2 3 4 5 6

Hours

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Contactor Temperature
Runaway Profiles

60/16
Temperature, F/C

A Temperature
50/10

40/4

30/-1 B Temperature

0 1 2 3 4 5 6
Hours

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Acid Runaway Response

Block in Olefin Feed


Continue Operation of Mixer
Continue Flushing With Isobutane
Retain All the Acid in the Reaction Zone
Spike Acid Into the Reactor
Obtain Acid Samples
Check Acid Strength and Stability
Determine the Cause
Post Excursion Inspection
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Sulfuric Acid Alkylation: Best Practice
Response to Acid Runaway
Acid
Sample OK

No

Excessive Acid Check for Other Symptoms: Physical Acid


Acid Strength >89%
in Suction Caustic Consumption, Settler Acid Level, Carry Over Likely:
Analysis Yes
Trap? High Acid Consumption Follow Procedures

Confirm With Spike Affected Check for Other Symptoms:


87-89% Another Sample, Contactor(s) With Temp. Drop in Contractor, Low Acid
Preferably From Fresh Acid and dp and Low Amps (Impeller), Sample
Contractor(s) Reduce Feed Wild Acid

Immediate Response
Block in Olefin Feed to Affected Contactor(s)
Bottle Up Affected Contactor/Settler
<87% (Do Not Remove Runaway Acid to Tankage)
Continue Operation of Contactor Mixer Follow Emergency
Procedures
Continue Flushing With Refrigerant Recycle
(Pascagoula: Freon System on With iC4 Recycle)
Spike Fresh Acid into Affected Contactor(s)
to Reconstitute Strength (88 Wt % Minimum)

Note 1: This Chart is Under Revision in 2002.


Note 2: All Acid Strength Numbers Are Assumed to Be +/-0.3 Wt % and
Based on Testing of Consecutive Samples.
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Possible Causes for Acid Runaway

Excessive Feed Contaminants


Excessive Feed Rate
Poor Contact
Inaccurate Fresh Acid Meter
Incorrect Fresh Acid Line Up
Low Acid to Hydrocarbon Ratio
Low Isobutane Concentration
High Reaction Temperatures
Start-Up (After Brief S/D) With Low Acid
Strength in Settlers
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Handling of Runaway Acid

Blend Off Runaway Acid Within Reaction System


(May Have to Raise Acid Levels in Settlers)
Monitor Runaway Spent Acid Tank Temperature
(Even a Few Degrees Increase Confirms Ongoing
Reaction)
Do Not Transfer Reactive or Low Strength Acid to
Rail Cars/Barges
Some Tanks Are Equipped With SO2 Neutralization
(El Segundo)

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Question and Answer Session

Q&A

Plus / Delta

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2. Acid Strength Discussion

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Some Things to Remember

Process Engineers May Give You the Wrong Acid


Concentrations for Your Corrosion Estimates. A Mixture of
50% Hydrocarbon, 40% H2SO4, 10% Water is 40% Acid to a
Process Engineer But the Acid Concentration on an Acid-
Water Basis is 80% [40/(40 + 10) = 0.80 = 80%]. 80% is the
Number to Use for Estimating Corrosion Rates and Materials
Performance.
Sulfuric Acid Readily Absorbs Water Which Dilutes the Acid
and Makes it More Corrosive to Steel. Small Leaks (e.g., Non
Seal-Welded Threaded Connections, Valve Packing, Etc.) Can
Quickly Lead to Large Failures.
Sulfuric Acid Corrosion (Formation of FeS Film, Not Active
Corrosion) Causes Hydrogen Gas to be Evolved This Can
Cause Pressure Buildup in Blocked Piping, Scab Patches, or
Improperly Vented Equipment. Also, Be Careful Cutting Into
Hydrogen Blisters!
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3. Corrosion of Carbon Steel by H2SO4

Confidential
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Corrosion of Carbon Steel by
Sulfuric Acid
Corrosion Rates Can Vary Substantially Depending
on Temperature, Acid Concentration, Turbulence,
and Velocity
Limit to 100F
Limit Velocities (Less Than 3 fps) and Minimize Turbulence
(Use Long Radius Bends of 5 Diameters or Greater, TIG Root
Passes, Beveled IDs at Pipe Joints of Dissimilar Schedules,
Watch Pipe Mismatch, Etc.)
Rates Are Lowest in 98% Acid and Can Increase
Dramatically in Acid Concentrations Below About 92% or
Above 99%

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Corrosion of Carbon Steel by
Sulfuric Acid (Contd)
Corrosion Can Be Highly Localized
Watch Ells and Straight Sections of Pipe After Multiple
Changes in Direction
Watch Piping Near Pumps and Just Downstream of Control/
Throttling Valves, Flow Orifices, Reducers, Etc.
Watch HAZs
Watch the 12 OClock Position in Horizontal Piping and
Nozzles, Especially Where Acid is Slow Moving or Stagnant
Watch the Interface Area in Tanks, Where Acid Can Be
Diluted by Drawn in Moist Air
Inspection
Supplement Conventional UT With Lots of RT (Shear Wave UT Can
Help Find HAZ Corrosion)
See Inspection Strategy IS-9

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Corrosion of Steel by
Sulfuric Acid
0.15
0.14 Corrosion of Steel by 150F Flange Quality Specifications
Sulfuric Acid Temp.
0.13 Carbon 0.25% Max.
80-150F
120F Manganese 0.30-.060%
0.12 Phosphorus 0.05% Max.
0.11 Sulfur 0.05% Max.
Inches Penetration Per Year

Steel Completely Immersed


0.10 Acid Not Stirred
0.09 Loss as Inches
Penetration/Year
0.08 100F
0.07
0.06
0.05
0.04 80F 150
120F F
0.03 120
F
0.02 80F 100
100F F
0.01 80F
0
50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66
Baum

62 64 68 72 76 80 84 88 92 94 96 98 100
Confidential
H2SO4, % Copyright 2002 by ChevronTexaco
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Corrosion Rate of Carbon Steel
in H2SO4
100
80F
100F
Corrosion Rate, mpy

80 120F
150F

60

40

20

0
90 92 94 96 98 100

Acid, %
Confidential
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Effect of Sulfuric Acid Concentration on
Carbon Steel Corrosion Rate
200F
100,000 150F
100F
10,000 75F
Mils Per Year, mpy

1,000

100

10

1
0 20 40 60 80 100
Sulfuric Acid, %

Confidential
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Iron and Steel
75F, Quiescent H2SO4

Confidential
G9601011 Copyright 2002 by ChevronTexaco
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Effect of Velocity on Carbon Steel
Corrosion
Corrosion Protection Comes From a Soft Film of
Ferrous Sulfate
This Film is Easily Disturbed
It is Fairly Easy to Diffuse Corrosives (Acid) Through
This Film
Common Historical ChevronTexaco and Industry
Guidelines Have Called for Velocity Limits of
1-3 fps
We Now Believe This Range is Too High Some in Industry
Say Should Restrict to 1 fps Maximum!
Even 2 fps Causes Turbulent Flow on Most Piping Systems
For Now, We Believe 0.5-2.0 fps is a Good Target Range

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Effect of Velocity on Corrosion in 95%
H2SO4 at 120F

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G9600990 Copyright 2002 by ChevronTexaco
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Typical Service Life of Acid Lines at
Ambient Temperature
(Source: T. F. Degnan, DuPont, June 1959)

Acid Strength (%) Velocity (fps) Service Life (Years)


93 0.4 10
93 3.5 5
93 6.5 3-5
98 1.0 15
98 6.7 1.5
99 11.9 1

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Carbon Steel Corrosion Rate Prediction
for 50-99% H2SO4
(From Dean & Grab, NACE Corrosion 98, Paper 147, April 1984)

Corrosion Depends Upon How Fast the Ferrous Sulfate


Corrosion Product Diffuses in H2SO4
Corrosion Rate
0.2 T 0.654 v 0.913 1.567
CR = (w S - w B )
1.221
d0.087
Where: CR is in mpy
T is in K
V is in fps
is in Lb/Ft3 (Density)
is in Centipoise (Viscosity)
d is in Inches (Pipe ID)
WS is in Mass % (Solubility of FeSO4 in H2SO4
WB is in Mass % (Amount of FeSO4 Already in the Acid)
Note the Importance of the Physical Nature of the Acid (Density
and Viscosity), and How Much Iron is in the Acid (How Hungry
It Is)
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Caution Watch Out for Severe Increases
in Temperature as H2SO4 is Diluted!

Initial Acid Final Final


Strength (%) Strength (%) Temperature (F)
93.2 77.7 244
93.2 62.2 268

98 77.7 310
98 62.2 287 (Boiling)

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Class Exercise

What is Your Inspection


Program for This Piping
System?
Be Specific in Describing
Where and How You Will
Inspect

Service: Acid Circulation


Temperature: 80F
Velocity 2-3 fps
Valve Material: Alloy 20
Pipe Materials: A-106B
and Alloy 20

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G020309 Copyright 2002 by ChevronTexaco
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4. Hydrogen Damage of Steel by H2SO4

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Hydrogen Damage

Hydrogen Damage in Alkylation Plants Comes in


Two Forms:
Atomic Hydrogen Can Be Changed Into Steel From the
Corrosion Reaction and Can Cause Blistering, HIC,
SOHIC, and, in Very Hard Steels, Hydrogen Stress
Cracking -- This Mechanism is the Same as Wet H2S
Type Damage
In Slow or Stagnant Acid, Hydrogen Bubbles That
Form at the Steel Surface Can Disrupt the Protective
Film and Promote Active Corrosion as the Molecules
Move Along the Top of a Pipe or Nozzle, or Up the
Shell of a Tank -- This Corrosion Mechanism is Called
Hydrogen Tracking

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Hydrogen Damage From H2SO4
Corrosion
The Mechanism is Similar to Hydrogen Damage Caused by Wet
H2S Corrosion However, Because Most Hydrogen Combines
at the Surface to Form Molecular Hydrogen and Because Iron
Sulfate Films Retard Corrosion, Hydrogen Damage in H2SO4
Services is Rarely Severe

Note: If the material corroding has high strength (>90 ksi, >Rc 22) then the hydrogen
charging can result in hydrogen stress cracking. B7 bolts have cracked in H2SO4 service.
Confidential
G9600991 Copyright 2002 by ChevronTexaco
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Hydrogen Grooving of Carbon Steel

Shallow
Circumferential
Grooves Toward
Top of Line Deep Groove at
Top of Line

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G9601009 Copyright 2002 by ChevronTexaco
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Hydrogen Grooving Corrosion

Hydrogen Grooving Corrosion on


Hydrogen Grooving Corrosion of 3 dia. Sidewall of Sulfuric Acid Storage Tank
Steel Elbow Elbow Was Sectioned and
View of Top 180 is Shown

Confidential
PR 960186-9,10 Copyright 2002 by ChevronTexaco
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Failed Nozzle From 98% Sulfuric Acid Tank
Nozzle Corroded Preferentially at the 12 Oclock Position

As Received Nozzle As Received Nozzle Split


Longitudinally

Confidential
PR 960186-5,6 Copyright 2002 by ChevronTexaco
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Class Exercise External Ultrasonic
Gage Points for a Sulfuric Acid Storage Tank
1. Which areas are most important to gage thoroughly?
2. Which Manway design is better, A or B? Why?
3. From a corrosion standpoint, is the fill nozzle located in a good place?

Vent
Fill Nozzle

Normal Acid Level

A - Manway
B - Manway
C Drain Nozzle

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5. Corrosion of Stainless Steels
by H2SO4

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Corrosion of Conventional Stainless
Steels by Sulfuric Acid
400 Series Stainless Steels Are Less Resistant Than Carbon Steel
Do Not Use Valves With 400 Series Trim in Sulfuric Acid Service
300 Series Stainless Steels Perform Erratically and Generally Do
Not Perform as Well as Alloy 20
300 Series Stainless Steels Can Perform Well in Very Dilute (<1%) and
Highly Concentrated (>93%) Acids, as Long as it is Ambient
Temperature
300 Series Stainless Steels With Molybdenum (e.g., 316L SS) Perform
Better Than Those Without Molybdenum (e.g., 304L SS)
316L SS Has Been Used Successfully as an Upgrade to Carbon Steel
But Alloy 20 is Always More Resistant and Alloy 20 Remains the
Minimum Acceptable Material for Many Components (e.g., Pump Seals
and Throttling Valves Where High Operating Temperatures and/or
Velocities Have Quickly Failed Carbon and Stainless Steels)
To Avoid Rapid, Localized Pitting, 300 Series Stainless Surfaces Must
Be Chloride-Free Before Being Contacted by Acid Rinse With Low
Chloride Water and Dry Before Acid Contact (See NACE RP 0391)
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Acid Corrosion of 300 Series SS Caustic Wash
Relief Valve Upgrade to Alloy 20

Corrosion on the 316SS Valve Plug Corrosion on the 304SS Valve Seat
Magnification Approximately 2x Magnification Approximately 2x

Confidential
PR 960186-7,8 Copyright 2002 by ChevronTexaco
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304 SS

100F
1,000,000 150F
175F
100,000
Corrosion Rate, mpy

200F
10,000
1,000
100
10
1
0.1
0 20 40 60 80 100
H2SO4, %

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316 SS

100F
1,000,000 150F
175F
100,000
Corrosion Rate, mpy

200F
10,000
1,000
100
10
1
0.1
0 20 40 60 80 100
H2SO4, %

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6. Alloy 20 in H2SO4

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Alloy 20 Development

1930s - Cast Material Developed


20% Cr 29% Ni 2.25% Mo 3.25% Cu Bal Fe
Alloy Content Has Never Changed!
1947 - Wrought Alloy 20 Introduced by Carpenter
Reduced Carbon Content by Introducing O2 to Melt
1948 - Wrought Alloy 20-Cb3 Introduced by Carpenter
Columbium Additions Stabilize Microstructure During Welding
Prevents Sensitization
1960s - Several Failures Occurred by Chloride Stress
Corrosion Cracking in H2SO4 Acid Solutions
1965 - Nickel Content of Wrought Material Increased to 34% to
Prevent SCC
Today
Cast Has No Cb & Lower Ni Than Wrought -- Therefore, It Has a
Slightly Lower Corrosion Resistance
All Wrought Alloy 20 is Alloy 20-Cb3 Confidential
Copyright 2002 by ChevronTexaco
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Alloy 20 in Sulfuric Acid

Alloy 20 is the Only Alloy Material Widely Used in


Sulfuric Acid Alkylation Plants and Has Performed
Well
Alloy 20 Resists Corrosion to All Concentrations of
Sulfuric Acid at Ambient and Slightly Elevated
Temperatures It is Not Immune to Corrosion; If the
Acid is Hot or Extremely Turbulent, Alloy 20 Will
Corrode
Similarly to Stainless Steels, it Protects Itself by
Forming a Passive Film

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Typical Iso-Corrosion Chart for Alloy 20
Cb-3 Stainless in Sulfuric Acid

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G9601094 Copyright 2002 by ChevronTexaco
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Typical Corrosion Resistance of Alloy 20 Cb-3
Stainless in Nonaerated Sulfuric Acid at 176F
(80C)

Confidential
G9601093 Copyright 2002 by ChevronTexaco
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Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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Corrosion of Alloy 20 Mixer From
El Segundos No. 1 Acid Treating Plant
Service: Jet Fuel and Concentrated H2SO4 at 120F

Confidential
PR 960439-2 Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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Class Exercise

1) Identify the Area of Worst Pipe Rack Orientation


Corrosion Flow Top
2) How Would You Inspect?

Bottom

Flow Flow

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Richmond Alkaline Water Wash Drum
Mix Point

Confidential
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Energy Research and Technology Company
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Richmond Alkaline Water Wash Drum
Mix Point

Flow
Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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04/03/02 mrb Sec3-6-G020306 Niccols
Richmond Alkaline Water Wash Drum
Mix Point

Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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7. Purchasing Requirements for
Alloy 20 Castings

Confidential
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Alloy 20 History

1935 Mars Fontana With DuPont Found That a Casting With 20%
Cr, 29% Ni, 2.25% Mo, and 3.25% Cu Had Superior H2SO4
Resistance Named it Alloy 20
1947-1948 Carpenter Improved Melting Techniques So That a
Wrought Version of Alloy 20 Could Be Formed, Carpenter 20 A
Year Later Columbium (Niobium) Added to Minimize Sensitization
1960 Alloy 20 Found to be Subject to SCC in 20-80% H2SO4, So Ni
Increased From 29% to 34% to Form Carpenter 20Cb-3
1970s-1980s ChevronTexaco and Others Developed Ordering
Descriptions and NDE Requirements to Try to Overcome Poor
Casting Quality and Sensitization Problems
1998 ASTM A 990 Approved Castings, Iron-Nickel-Chromium and
Nickel Alloys, Specially Controlled for Pressure Retaining Parts for
Corrosive Service
Note the Unified Numbering Series Number for Alloy 20 is UNS
NO8020 Confidential
Copyright 2002 by ChevronTexaco
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Sensitization

Carbides

Chromium
Depleted
Zones
Grain
Boundaries

Confidential
G9601606 Copyright 2002 by ChevronTexaco
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Cracked Pump Case From El Segundo
Case Was Sensitized Due to Improper Heat
Treatment Despite Presence of Cb
Inner Surface of Pump

Alloy 20 Cb-3 Boat Sample From P-26


Showing Cracks Which Are From
Intergranular Corrosion

Cross-Sectional View of Cracking


Caused by Intergranular
Corrosion of P-26 Oxalic Acid Etch
(Magnification 200x)
Confidential
PER 960186-1, 2 Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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SEM Micrograph Showing a Grain Boundary of El Segundo
P-26 Alloy 20 Cb-3 Pump Case and the Chromium Concentration
Variations Associated With That Boundary

Oxalic Acid Etch (Magnification 2500x)

A. Matrix Cr = 22.5%

B. Precipitate Free Zone Cr = 9.5%


C
C. Chromium-Rich Carbide

D. Columbium Carbide

Confidential
PER 960439-1 Copyright 2002 by ChevronTexaco
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Purchasing Requirements for Alloy 20
Castings: Pre-A 990
Chevron Purchasing Requirements (Historical See ERTC for Details)
1. No Cb Added (Makes Casting Difficult, Primarily an Issue With
Large Castings Such as Pumps)
2. Carbon Content of No Greater Than 0.03%
3. Use Carbon-Free Molds
4. Heat Treat as 2050F Minimum for -Hour Per Inch of Thickness,
1 Hour Minimum, Followed by a Water Quench
5. Specify Supplementary Requirement ASTM A 744 S21.1 The
ASTM A 262 Practice B Sensitization Test Should Be Performed
(Test Corrosion Rates of Less Than 30 mpy Are Considered
Acceptable)
Notes
(1) Sensitization is Not a Problem for Cb Stabilized Wrought Alloy 20
(2) For Existing Sensitized Alloy 20 Castings, Belzona-Type Repairs of
Minor Cracking Are Probably Better Than Attempting Weld Repairs
Confidential
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Purchasing Requirements for Alloy 20
Castings = Today
Much Prefer to Use Modern A990 Casting Spec
(Grade Designation CN3MCu). This Allows Us to Use
a Standard Specification Without Additional
ChevronTexaco Requirements, Rather Than the
Older Specs A 351 or A 744 Plus Many Additional
Requirements.
A 990 Requires Secondary Refining of the Melt by
AOD (Argon Oxygen Decarburization) or VOD
(Vacuum Oxygen Decarburization) Processes. This
Produces Much Lower C, S, Etc., Cleaner Steel,
Easily Meeting ChevronTexaco Requirements. No
Sensitization, Much Less Cracking, Much Easier to
Weld Repair.
We Are Trying to Push the Alloy 20 Casting
Suppliers to A 990 Confidential
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8. Welding Alloy 20 Cb-3

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Preventing Hot Short Cracking in
Alloy 20 Cb-3
Use Electrodes Low in Sulfur and Phosphorous
(E320LR-15)
Use Weld Procedures That Minimize Heat Input and
Produce Rapid Cooling
Use Small Diameter Electrodes
Cool Between Passes to Below 200F

Confidential
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Hot Short Cracking in Alloy 20 Cb-3
Thermowell Weld Crack Resulted in
In-Service Fatigue Failure

Failed Alloy 20 Thermowells Section of Crack Was Through the Centerline at the
Completely Failed Thermowell (Top), Weld Magnification 5x
Partially Cracked Thermowell
(Bottom Arrow Points to Crack)

Confidential
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End Preparation for Pipe of
Unequal Wall Thickness

Confidential
G9600893 Copyright 2002 by ChevronTexaco
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9. Nickel-Based Alloys in H2SO4

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Nickel-Based Alloys in Sulfuric Acid

Hastelloy B and Hastelloy C276 Have Very Good


Resistance and Are Used as an Upgrade to Alloy 20
in Circumstances When Alloy 20 Corrodes
Hastelloy B is More Resistant to H2SO4 Acid Than
Hastelloy C276 Except in Hot Dilute Sulfuric Acid
The Corrosion Resistance of Hastelloy B is
Influenced by Contaminants

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HASTELLOY Alloy B-2
Resistance to Sulfuric Acid

*All test specimens were solution heat-treated and in the unwelded condition.

Confidential
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HASTELLOY Alloy C-276
Resistance to Sulfuric Acid

*All test specimens were solution heat-treated and in the unwelded condition.

Confidential
G9601096 Copyright 2002 by ChevronTexaco
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10. Other Metals in H2SO4

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Other Metals in Sulfuric Acid Service

Lead Has Good Corrosion Resistance to All Acid Concentrations


But Forms a Poorly Adhering Sulfate Film That is Easily Removed,
Even at Low Velocities. Lead is Not Used Anymore, Primarily Due
to Environmental/Health Concerns.
Copper Alloys Do Not Resist Concentrated Acid, But Are More
Resistant Than Steel to Corrosion by Dilute Acid This Can Be
Useful in Distillation Overhead Systems Where Trace Acidity is
Sometimes Present (Watch Sulfate SCC of Admiralty). The
Presence of Air Greatly Accelerates Corrosion.
Monel Behaves Similarly to the Copper Alloys
Cast Irons, Especially Those High in Silicon, Can Be Very
Resistant to Corrosion But Are Seldom Used Due to Their
Brittleness Ni-Resist Type 1 (15.5 Ni, 6.5 Cu, 2.5 Cr) Has Been
Used for Contactor Impellers.
Titanium and Zirconium, Which Performs So Well in Many
Aggressive Environments, Can Corrode Rapidly in Sulfuric Acid,
Especially Concentrated Acid. Performance Can Be Good in
Dilute Acid. Confidential
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Corrosion in Dilute H2SO4 200F

Confidential
G020332 Copyright 2002 by ChevronTexaco
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Estimate of Corrosion Rates in Dilute
Sulfuric Acid (Continuous Immersion)
Ambient
Temperature, mpy 150F, mpy
Carbon Steel >500 >1700
316L Stainless Steel <5 <5*
Monel 400 <30 <90
Alloy 20-Cb3 <5 <5
Hastelloy G-30 <5 <5
Hastelloy C276 <5 <5

*These Are General Corrosion Rates for Continuous


Immersion of 316 SS With No Chlorides Present Chlorides
Can Pit 316 SS Very Quickly
Confidential
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Sulfate SSC of Admiralty in
DIB Overhead

Confidential
PR 960437-2, 3 Copyright 2002 by ChevronTexaco
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Corrosion of Ni-Resist (Type 1) in
Sulfuric Acid Temperature 86F

Confidential
G9601091 Copyright 2002 by ChevronTexaco
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11. Summary of Metallic Materials for
H2SO4 Service

Confidential
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Flake Type Ni-Resist Alloys

Ni Cr Cu Si Mn C Fe

NiMn 13 7 12-14 0.2 Max. ---- 1.5-3 6-7 3.0 Max. Balance

Type 1 13.5-17.5 1.75-2.5 5.5-7.5 1-2.8 1-1.5 3.0 Max. Balance

Type 1B - Erosion
13.5-17.5 2.75-3.5 5.5-7.5 1-2.8 1-1.5 3.0 Max. Balance
Resistant

Type 2 - 20% Nickel 18-22 2.75-3.5 0.50 Max. 1-2.8 0.5-1.5 3.0 Max. Balance

Type 2B - Heat Resistant 18-22 3-6 0.50 Max. 1-2.5 0.5-1.5 3.0 Max. Balance

Nicrosil-al 18-22 1.5-4.5 ---- 3.5-5.5 0.5-1.5 3.0 Max. Balance

Type 3 - 30% Nickel 28-32 2.5-3.5 0.50 Max. 1-2 0.4-0.8 2.60 Max. Balance

Type 4 - Heat & Stain


29-32 4.5-5.5 0.50 Max. 5-6 0.4-0.8 2.60 Max. Balance
Resistant

Type 5 - Minovar 34-36 0.10 Max. 0.50 Max. 1-2 0.4-0.8 2.40 Max. Balance

Type 6 18-22 1-2 3.5-5.5 1.5-2.5 0.5-1.5 3.0 Max. Balance

*There Are Just as Many Ductile Type Ni-Resist Alloys Confidential


Copyright 2002 by ChevronTexaco
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Effect of Velocity on Corrosion
of Ni-Resist
700

600

500
Corrosion Rate, mpy

Agitated 15.5 ft/min (0.26 fps)


400
Quiescent
300

200

100
Temperature: 194F
0
80 85 90 95 100
H2SO4Concentration, %
Confidential
Copyright 2002 by ChevronTexaco
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Chemical Compositions and
Specifications for Alloys Used in Sulfuric
Acid Service

Generic UNS Component ASTM Chemical Composition


Designation No. Type Specification Al C Co Cr Cb Cu Fe Mn Mo
AISI 316L S31603 Pipe A312 TP316L or A358 0.03 Max. 16-18 Rem 2 Max. 2-3
316L Class 1

ACI CF-3M (316L J92800 Casting A744 CF-3M 0.03 Max. 17-21 Rem 1.5 Max. 2-3
Casting)

Alloy 20 Cb-3 N08020 Pipe B474 NO8020 Type 1 0.07 Max. 19-21 8XC-1 3-4 Rem 2 Max. 2-3
or B464 N08020

ACI CN-7M (Alloy 20 J95150 Casting A744 CN-7M or A351 0.07 Max. 19-22 3-4 Rem 1.5 Max. 2-3
Casting) (N08007) (See Special (0.03
Chevron Chevron)
Requirements)

Hastelloy C-276 N10276 Pipe B622 N10276 or B619 0.02 Max. 2.5 Max. 14.5- 4-7 1 Max. 15-17
N10276 Class 1 16.5

CW-12MW (C-276 - Casting A494 CW-12MW 0.12 Max. 15.5- 4.5-7.5. 1 Max. 16-18
Casting) Class 1 17.5

Hastelloy B-3 N10665 Pipe B622 N10665 or B619 0.05 Max. 1 Max. 1 Max. 2 Max. 1 Max. 26-30
N10665 Class 1

N-7M (B Casting) - Casting A494 N-7M Class 1 0.12 Max. 1 Max. 3 Max. 1 Max. 30-33

Confidential
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04/03/02 mrb Sec3-11-G020306 Niccols
Chemical Compositions and
Specifications for Alloys Used in Sulfuric
Acid Service (Contd)
Generic UNS Component ASTM Chemical Composition
Designation No. Type Specification N Ni P S Si V W Ti
AISI 316L S31603 Pipe A312 TP316L or A358 10-15 0.045 Max. 0.03 Max. 0.75 Max.
316L Class 1

ACI CF-3M (316L J92800 Casting A744 CF-3M 9-13 0.04 Max. 0.04 Max. 1.5 Max.
Casting)

Alloy 20 Cb-3 N08020 Pipe B474 NO8020 Type 1 32-38 0.045 Max. 0.035 Max. 1 Max.
or B464 N08020

ACI CN-7M (Alloy 20 J95150 Casting A744 CN-7M (See 27.5-30.5 0.04 Max. 0.04 Max. 1.5 Max.
Casting) Special Chevron
Requirements)

Hastelloy C-276 N10276 Pipe B622 N10276 or B619 Rem 0.04 Max. 0.03 Max. 0.08 Max. 0.35 3-4.5
N10276 Class 1 Max.

CW-12MW (C-276 - Casting A494 CW-12MW Rem 0.04 Max. 0.03 Max. 1 Max. 0.2-0.4 3.75-
Casting) Class 1 5.25

Hastelloy B-3 N10665 Pipe B622 N10665 or B619 Rem 0.04 Max. 0.03 Max. 0.1 Max.
N10665 Class 1

N-7M (B Casting) - Casting A494 N-7M Class 1 Rem 0.04 Max. 0.03 Max. 1 Max.

Confidential
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Corrosion Rates of Various Alloys
in Sulfuric Acid at 100F
3000
CS
304SS
2500
316SS
Alloy 20
Corrosion Rate, mpy

2000

1500

1000

500

0
0 10 20 30 40 50 60 70 80 90 100
Sulfuric Acid Concentration, % Confidential
Copyright 2002 by ChevronTexaco
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Corrosion Resistance of Materials to
Sulfuric Acid
Corrosion Rate Less Than 0.020 Inches Per Year

Confidential
G9601007 Copyright 2002 by ChevronTexaco
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12. Nonmetallics in H2SO4

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04/03/02 mrb Sec3-12-G020306 Niccols
Nonmetallics in Sulfuric Acid

Polypropylene (PP), Polyvinyl Chloride (PVC), and Low Density


Polyethylene Can Experience Environmental Cracking in Sulfuric
Acid High Density Polyethylene is OK
Polyester, Vinyl Ester, and Epoxy-Based Fiberglass Piping
Systems and Epoxy-Based Coatings Are Readily Attacked by
Concentrated Acid Some Epoxy Novolac Coatings Can Perform
Well (Contact ERTCs Paul Hunter)
High Temperature-Baked Phenolic Coatings Can Provide Good
Long-Term Service in 90-98% Acid When Properly Applied and
Cured
The Fluorinated Plastics (e.g., Teflon and Kynar) Perform Well Over
a Wide Range of Acid Concentrations and Temperatures Teflon is
an Industry Standard Gasket and Valve Packing Material (For Valve
Packing, Specify Braided Teflon, Free of Graphite Binders; e.g.,
John Crane 1045)
Pure Carbon and Impervious Graphite (e.g., Karbate) Resist Acid
Up to Concentrations of About 96% -- Chevron Uses Karbate in Tail
Gas Plants, Not Alky Plants Confidential
Copyright 2002 by ChevronTexaco
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Suitability of Plastic-Lined Piping
Systems in Sulfuric Acid
Maximum Concentration
Material Temperature, F Sulfuric Acid, %
PVDC Saran 125 <16
75 30
NR >60
PP Polypropylene (Can 200 <60
Experience Environmental 175 93
Cracking) 145 96
120 98
PDVF Kynar 250 <16
220 30-60
175 85-93
145 94-98
TFE Teflon 500 0-100
*Temperature May Be Further Limited by Mechanical Conditions Under Vacuum
Source: Dow Chemical, Midland, Michigan
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13. Corrosion Under Insulation/
Some Things to Remember

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Corrosion Under Insulation (CUI)

Characteristics
Equipment Operating Up to 250-300F is Susceptible Equipment
in Intermittent Service is Particularly Susceptible (Intermittent
Means More Than ~10% of the Time Below 250-300F)
CUI is More of a Problem in Humid Climates But Almost All Our
Refineries Have Experienced CUI Failures Equipment Operating
at Subambient Temperatures and Equipment Exposed to Cooling
Tower Drifts Are Susceptible Regardless of Climate
Corrosion is Typically Worse Under Fibrous Insulations Like
Fiberglass or Mineral Wool Closed Cell, Water-Resistant
Insulation Like Cellular Glass or Perlite is Usually Best for CUI
Prevention (Polyurethane Foam is an Exception); Calcium Silicate
is Somewhere in Between. Corrosion Also Occurs Under Fire-
Proofing.
Both Carbon Steel and Stainless Are Susceptible to CUI With
SS, the Primary Concern is Chloride SCC
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Corrosion Under Insulation (CUI)
(Contd)
Corrosion is Highly Localized Examine the
Equipment/Piping System Carefully to Identify Likely CUI
Spots In Particular, Look at:
Flanges in Vertical Pipe Runs
Low Points in Vertical Piping
The 6 OClock Position on Horizontal Exchanger Shells
The Area Just Above Insulation Support Rings on Vessels
Damaged Weather Jacketing
Insulation Cut Outs
Bulged Weather Jacketing
In Alkylation Plants, CUI is Most Prevalent in the Refrigerated
(Subambient) Sections of the Plant

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Corrosion Under Insulation (CUI)
(Contd)
Prevention
Maintain Weather Jacketing in Good Condition
Apply Coatings to CS and SS Surfaces (See Coatings Manual)
Epoxy for Lower Temperatures
Polysiloxanes for Higher Temperatures
Remove Insulation Where Its Not Necessary For Personnel
Protection, Use Expanded Metal Instead of Insulation

Confidential
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Corrosion Under Insulation (CUI)
(Contd)
Inspection
See Inspection Strategy IS-19
Comply With API 570 Paragraph 4.3
Typical Techniques Include:
UT at Cut Outs
Spot Stripping and UT
Radiography
Real Time X-Ray
Real Time Radiography (New Technique Recently Tried
at Cedar Bayou)

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Corrosion Under Insulation

Pipe Mastic Cracked or Water Enters if Pipe


Insulation Burned Away From Line Seal is Not Tight
Water Band Aluminum
Enters Cap
Insulation

A. Weatherjacket Overlap B. Deteriorated Mastic C. Poor End Seal on


Pointing Upwards Seal Vertical Line
Concave Downward so
it Collects Water Which
Runs in at Overlap Platform Supports,
Lines, Etc.

Vessel Head
Vessel
Head
Lines, Ladder,
Supports, Etc.

D. Insulation Improperly Boxed E. Unsealed Penetrations Through


Around Vessel Stiffening Ring Weatherjacket
Confidential
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Confidential
Copyright 2002 by ChevronTexaco
Energy Research and Technology Company
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04/03/02 mrb Section13-G020306 Niccols
Confidential
Copyright 2002 by ChevronTexaco
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14. Brittle Fracture

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Brittle Fracture

As They Get Colder, Carbon and Low Alloy Steels Undergo a


Ductile-to-Brittle Transformation and Become Susceptible to
Brittle Fracture
Susceptibility to Brittle Fracture is Dependent on:
Material Properties Wrought, Heat Treated (e.g., Normalized,
Quenched and Tempered) and Fine Grained Steels Are Less
Susceptible Than Cast, as Rolled or Coarse Grained Steels. Newer
Steels Are Less Susceptible Than Older Dirty Steels.
Applied Stress Brittle Fracture is Not a Concern When Applied
Stress is Less Than 8 ksi. The Greatest Concern for Brittle
Fracture is With Pressure Vessels and Tanks, Not Piping
Components. Vessels Operating Near Full Design Pressure Are
More Susceptible Than Those Operating Well Below Design.
Presence of Flaws Flaws Concentrate Local Stresses and Can
Greatly Increase Susceptibility to Fracture
Temperature Lower Temperatures Increase Risk

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Charpy V-Notch Energy Absorption
of A36 Steel

Confidential
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Brittle Fracture of a Chevron LPG Vessel
Clear Creek, Wyoming

Top Head Shell Section

Confidential
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Minimum Pressurizing Temperature
(MPT or MAT)
When the Metal Temperature is Below the MPT:
Material Do Not Apply More Than
Section VIII, Div. 1, 40% of Maximum Allowable
Built Pre-1999 Working Pressure
Section VIII, Div. 1, 35% of Maximum Allowable
Built 1999 & Later Working Pressure
Section VIII, Div. 2 25% of Design Pressure

For New Vessels, the Fabricator Assigns a Minimum Design Metal


Temperature per the Code

The User Assigns a MPT to Take Into Account Possible Service


Degradation of Toughness -- Degradation is Unusual for Carbon Steels,
But Common for Cr-Mo and Alloy Steels (Consult Materials Specialists)

The New API RP 579 Fitness for Service Document Uses the
Terminology Minimum Acceptable Temperature (MAT)
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ASME, Section VIII, Division 1 Curve
Assignments (Reprinted From
Fig. UCS-66 of the ASME Code, Div. 1)

Example Only
See the Corrosion
Prevention &
Metallurgy Manual for
Actual Curves.

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Chevron Special Material Assignments
to Curves

ASME Code Chevron


(All Thicknesses) 3/4 >3/4
SA-285 Grade A B B A
Grade B B B A
Grade C A A A
SA-515 Grade 60 B B A
Grade 65 A A A
Grade 70 A A A
SA-106 All Grades B B A
SA-53 All Grades B B A

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Some Typical Vessel Details Showing
the Governing Thicknesses

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Some Typical Vessel Details Showing
the Governing Thicknesses (Continued)

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Some Typical Vessel Details Showing
the Governing Thicknesses (Continued)

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Isothermal Lines of Lowest One-Day Mean
Temperatures (From API Standard 650)

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Autorefrigeration

Applies to LPG Services


Rapid Vaporization Due to a Leak or
Depressurization Can Cause Cooling Below Ambient
MDMT Needs to be Equal to Vaporization
Temperature of Liquid Stock for P = 35-40% of
MAWP (i.e., About 8 ksi Membrane Stress)
Consult With CRTC Materials Engineers and Process
Engineers Regarding MDMTs for LPG Service --
Always a Level 3 Analysis

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Confidential
Copyright 2002 by ChevronTexaco
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Chevron Policy on MDMTs (MPTs) for
New and Existing Equipment
New Equipment
z MDMTs Always Meet Applicable Code (+ Year) of Construction, Plus
Additional Requirements in CPM Section 340 (Included in Chevron
Pressure Vessel and Piping Specs)
Old/Existing Equipment
z MPTs Established Per Prior Chevron Policies Previously in Effect Are
Still Acceptable Unless Specifically Rescinded (1969 Curves; 1983
Curves)
z Chevron Adopting API RP-579 Section 3 With Restrictions Per CPM
Section 340
Consult Materials Specialists
z For Level 2 and 3 Analyses

z For 1% Cr and Higher Alloys (In-Service Embrittlement)

z For Autorefrigeration Cases and LPG

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MPTs Precautions, Things to
Remember
If an MPT is Higher Than the Lowest 1-Day Mean Temperature at Your Location,
Then Operating Precautions (e.g., Preheating Prior to Full Pressurization) May
Be Needed
MPTs (MDMTs) Provided by Equipment Manufacturers or Determined by Code
Curves Are Not Applicable to Vessel Metallurgies Which Embrittle During
Service (e.g., 1-1/4 Cr and 2-1/4 Cr Reactors, Exchangers) Chevron Has
Assigned Special MPTs for These Vessels and Operating Restrictions Are
Necessary to Avoid Brittle Fracture
For Hydrotesting, Metal Temperatures Should Be 30F Higher Than the MPT as
an Added Precaution (But Dont Use Water Hotter Than 120F)
Repressurizing Immediately After an Autorefrigeration Event Poses a Danger
Even to Relatively Tough Steels
Chevron is Sometimes More Conservative Than the Code
A285 and A515 Steels >3/4-In. Should Go on UCS 66 Curve A, Not B
A106 >3/4-In. Should Go on Curve A, Not Curve B, Unless Normalized

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Whats the MPT for This
Section VIII Division 1 Vessel?

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15. Caustic Cracking and Corrosion

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Caustic Cracking and Corrosion

Caustic Cracking and Corrosion Can Be a Problem


During the Following Upsets:
Large Quantities of Acid Are Carried Into a Caustic or
Alkaline Water Washer and the Heat of Reaction Exceeds the
Threshold for Cracking
Caustic is Carried Into Downstream Equipment (e.g., DIB
and Depropanizer Feed Heaters) Where Temperatures
Exceed 140F
Lines Containing Caustic Are Heat Traced -- Note: Do Not
Let Heat Tracing Directly Contact the Caustic Piping
Caustic Cracking and Corrosion Can Also Occur in the
Recycle Loop of the Caustic or Alkaline Water Wash
Drums This Temperature Has Been Increased in Recent
Years to Help Break Down Acid Esters
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Relation of Temperature and Concentration of
NaOH to Cause Cracking NACE Data

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Recommended Limits of CS and SS
in NaOH Service
Temperature, F
240
Area C Area C CS
220 and SS
Not Adequate

200

180

160 Area B Stress Relief Recommended

140

120

100
Area A Stress Relief Not Required

80
0 10 20 30 40 50 Confidential
NaOH, Wt % Copyright 2002 by ChevronTexaco
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Corrosion of Carbon Steel by
Sodium Hydroxide

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