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. Ammonium bi-sulphide ::;11<


REFINING

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1t/ifItjjJ;:~:(\ 'G:t4(P::e:;':4:4 ,p.J.'tD:J- . .

corrosion in hydrocrackers
Factors in the corrosion of effluent condensers in hydrocrackers are the
subject of this artiele, which ineludes a case study of the problems experienced
at Riyadh refinery, Saudi Arabia, and the corrective actions that were taken
Walid A Al-Naim
Saudi Arameo

orldwide hydrocracker opera


tional experience has drawn
attention to unique corros ion
problem that is . developing in reactor's
effluent condensers. This corros ion prob
....m is defined as ammonium bi-sulphide
.
H 4 (H5)) corrosion. Ammonium bi-sul
phide corrosion is considered very risky
and may lead to a catastrophe because
hydrocrackers operate at high pressure,
high tempera~e, and in a hydrogen
atmosphere. Numerous incidents of efflu
ent condenser failures and consequent
fires have been experienced in a number
of refineries around the world due to this
form of corrosion.
Ammonium bi-sulphide's inherent
corrosivity is a function of the organic
nitrogen (pyridines, quinolines, and
acridines) and sulphur (thiophene,
benzo and di-benzo-thiophene) content
in the hydrocracker fresh feed that is
finally corrcrted intc Nll 3 al1d H2S in
the hydrotreating reactors. As organic
sulphur and nitro gen levels increase in
the fresh feed to the hydrocracker, more
ammonium bi-sulphide is produced,
A ading to corrosion attack in the efflu
~nt ~ondenser...
The ammonium bi-sulphide corrosion
is further wors~ned when hydrocracker
feed is heavier than the conventional vac
uum gasoil (VGO) feed. An example of
heavier feed stock is VGO with demet
allised oil (DMO > 1050F) feed which
contains high levels of organic nitrogen,
and asphaltene which is a precursor to
carbon lay down on the catalyst.

NH 4 (HS) formation
Ainmonium bi-sulphide corros ion is con
sidered a main source of potential hazard
to hydrocrackers in all parts of the world.
T~e recipitation of the ammonium bi
sulphide on t e effluent con enser tu es
causes under-deposit corrosin and tube
pitting. Thereafter, condenser failure is
bouna to occur, with a potential disaster.
A AS a result, remedial mea sures and correc
. .ive actions at design stages and unit oper-

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Figure 1 Impact of Kp factor on ammonium bi-sulphide formation

ation re being take!1 and implementecl in


an attempt to mitigate this phenomenon
as much as possible and thereby ensuring
the plant safety and integrity. Hydroc
racker operational experience has led to
the identification of several parameters
that are considered as driving forces for
ammonium bi-sulphide corrosion attack,
as listed in Table 1.
The table shows the optimum parame
ters to operate the hydrocracker reactor
effluent condenser free from ammonium
bi-sulphide attack. These values were
brought into practice after extensive sur-

Optimum parameters
~~

Optimum
value

Operational
parameters

1. Piehi Kp Factor
0.15
2. NH.(HS) wt % in wash water 4.8
3. Wash water rate, vol% leed
5.2
4. Oxygen (ppm) in wash water 0.05
5_Condenser tube velocity, Ips
15

veys and experi~nducted by NACE

and analysed b~

Effect of Kp factor

The levels of nitrogen and sulphur con

tent in feedstocks mainly dictate the

extent of ammonium bi-sulphide forma

tion in the reactor effluent condenser. In

hydrc-processing plants that process

heavy feed stocks such as VGO and DMO,

NH 3 and HzS are produced in fairly high

concentrations, leading to a highKp fac

tor (mol% NH3 x mol% H2S).

The ammonium bi-sulphide fouling


rate at the effluent condenser is classified
as severe, modera te, and low based on the
Kp factor levels. The severity of corrosion
is indicated as follows:
Kp > 0.5
Severe (5)
Modera~e (M)
Kp < 0.15
Low (L)
Kp < 0.07
Since the Kp factor has a critical impact
on the ammonium bi-sulphide forma
hon, it is essential that the refiner oper
.ates his plant at the original design rates
in order to maintajn the NH.L~n--Jjz.S
concentrations at the safe leveJj at

which they can be controTied-through

Table 1

45
PTQ WINTER 1999/2000

REFINING
other proces' p~rameters . Moreover,
th,e Kp factor dicta tes how much high
er is the effluent condenser outlet tem
perature than the temperature at
which ammonium bi-sulphide starts
crystallising, as shown in Figure 1 (on
previous page).
The higher the ammonjum ru-sul
QEidt concentratjon, tbe higher the
condenser outlet temperatme sbollld be,
to avoid NH,(HS) crystallisation. In
essence, it is a very important factor dur
ing the design stage of the effluent con
denser to be capable of controlling the
outlet temperature, taking into account
feed rate and quality (organic N:! and
sulphur cantent) oscillations.

Effect of wash water system

f. .

. .. ,

I
' . .\ ,

i 41
I
,

Water injection is intended to perform


the dual function of removing the
NH,(HS) from the system to avoid tube
plugging and to reduce the corrosivity
of the medium by minimising the con
centration of NH,(HS) in the liquid
phase. Therefore, the water injection
point, rate,and quality have to be opti- .
mised in order to reduce the extent of
ammonium bi-sulphlde corrosion.
1. Water..injection poinl Wash water ha~
to be injected into the common line
upstream of the effluent condenser in
order to ensure even distribution of
the wash water among all condenser
bani<s provided the temperature at
this point is sufficient to vaporise
most of the water.
If the water does not vaporise at the
~ould be injected
through separate connections iillo
each individual condenser bundle,
and restriction orifices should be used
to assure good distribution.
On the other hand, it is recommended
that 20 per cent oE the injected ~~r_
remains in the aq ue'?Y~_J2.J:1~s~_. t
avoid an acidic dew poin! corrosion
wb.~.re the first drop oE condensed
water wiII have high ammonium bi
sulphide concentration, leading to an
acidic attack in the condenser tubes
and piping.
2. Water injection rate. The rate of water
injection should be adequate enough
to maintain the concentration of
NHi(HSl in theTnjection water not to
exceed 5 wt%. In practice, the wash
water in'ection rate should be within
-8 LV% f the unit fresh feed . This
rosi-v'ity of ammonium bi-sulphide
and to wash off the deposited salts.
3. Water injection quality. Practical
experience recommends that clean
steam condensate be used as ;as:
water injection for the effluent con
denser to eradicate any source of
potential corrosion attack other than
amm o nium bi-sulphide co rros ion.

Figure 2 Original design of the effluent condenser


For instance, if the wash water con- and minimise the differences in fluid
tains traces of chloride, amm~velocity from one bank to another, as
. c hloride will form as a result, causing well as maintain consistent corrosion
another severe corrosion attack in rates on the entire surface of the con
combination with ammonium bi-sul- denser tubes, thereby prolonging the
phide .
condenser run time.
In addition, the presence ofoxygen irGEffect of fluid velocity
the condenser will accelerate any corro
The effluent condenser tubes and piping
sion problems that may existo The most Circuit should be designed in compli
likely source of oxygen is the wash water ance with the recommended velocity of
itself. In many instances, water is ~ for carbon steel material.
pumped into the system from an open The 1976 NACE survey indicated that
tank, in which case it may contain velocity is an important corrosion vari
about 1-10ppm of oxygen . Water injec
able and that severe corrosion/erosion
tion tanks should be covered and blan
attack is likely to happen at velocities oE
keted with an inert gas, and <2.!l!Y... more than 20ft/sec . In that case, the
d~~rated water can be used as wash effluent condenser p.!pj_~_g...9 !:.cuit, head
water for the effluent condenser.
er boxes, return b ~ nds, tubes and outlet
Effect of piping syrnmetry
n02:7.les \... iIl ell.peri'O'I!('e irr..pingement
During design stages oE new hydrocrack
erosiOn aY ac
coiripounded wlth
ing units, it is vital to ensure the sym
ammonium'bi-ru IPhide ~orrosi~~-
metry of the inlet and outlet piping..Qf Effect of temperature co ntrol
~he eftluent condenser. This will achieve
In addition to the abo ve, control over
equal distribution oE oil, water, and
the effIuent condenser outlet temp~a
vapour phases between condenser banks !~ has a direct impact on the extent

Figure 3 Effluent condenser location after the revamp

46
PTQ WINTER 1999/ 2000

REFINING
eonncnsers:
2 Tube material: killed es
Parallel b:nks: 8
Header box: killed es
Tube passes:
3
Tube diameter: lin
Tubes per pass:62
Return bends: No
As anticipated, this revamp helped to
mitigate the HPNA plugging problems,
and also enhanced ammonium bi-sul
phide corrosion by upsetting the original
design parameters of the effluent con
denser. Figure 3 shows the new location
for the effluent condenser.

Revamp consequences

Figure 4 Hydraulic un-symmetry

of the subject corrosion attack. The


direct relationship between the Kp fac
tor and the temperature, as shown in
~ t) dictates that the effluent con~
den:ser'outlet temperature be higher
than the temperature at which ammo
nium bl-sulphide crystals form (50C) .
This problem becomes more acute
during winter when control of the efflu
ent condenser outlet temperature is dif
ficult. However, recent studies have
established that variable speed motor
driven fans are very efficient in this ser
vice. This tec:hnology bocsts the effluent
condenser flexibili ty in handling the
seasonal ambient temperature change
along with the feed rates and quality
variations.

Case study
Riyad/l refinery experience with
NHlHS) coTTosion

Riyadh refinery hydrocracker is a uOP


designed unit, commissioned in 1981.
The unit is designed to prccess (luout
'. 30000bpdof a combination of heavy
feeds, as follows :
- Vacuum gasoil
- De-metallised oil from a UOP butane
de-asphalting unit (vacuum residue raffi
nate from a Demex unit).
The unit comprises two trains of two
stage series flow reactors with one recy
ele compressor and three make
com'pressors. It u tilises hydrotrcating/
hydrocracking amorphous catalyst in
the first stage and hydrocracking zeolte
catalyst in the second stage. To prevent
H 2S/0leins recombination reaction, the
process also utilses a post-treatment
catalyst at the bottom of the Iast reactor
of the second stage.
The unit was revamped to utilise an
indirect recycle mode and to utilise the
high pressure separator as a hot separa
tor in order to alleviate HPNA buildup
problem.

Kp factor ncrease
The KJ2 factor in the effluent condenser
has increased by 42 ger cent as compared
with the pre-revamp value. Since NH J
and H2S rema in in the ~lL-liiii~~
-de crease 10 the molar flow rate ioto tlle
effluent condenser (compared with the
pre-revamp situation where the entire
reactor effluent was processed into the
condenser) has resulted in an increase of
Hydrocracker unit history
Excessive HPNA formation at the NH J and H2S concenriations in the con
~nser, thus creating a higher Kp factor .
effluent condenser
For many years, Saudi Arameo Riyadh Uncontrollable outlet temperature
refinery has suffered greatly from an In addition to the increase in the Kp fac
ammonium bi-sulphide corrosion prob
tor, the lower molar flow rate inside the
which was originally
lero taking place in the hydrocracker condenser,
reactors effluent condenser, causing 1055 designed with a higher surface area, has
of production, increased maintenance consequently reduced the fluid velocity
cost, unit upsets, and potential hazard.
to below 10--20ft/sec at which overcool
However, prior to the appearance of ing of the vapour to below 50C is evi
this problem, Riyadh refinery was suffer
dent. Additionally, this velocity is low
ing from HPNA buildup in the effluent enough for the ammonium bi-sulphide
condensers, which required unit shut
to settle down in the tubes, causing pit
down for about one week, four to five ting and under-deposit corros ion.
times during ea eh cycle for tube clean
The average seasonal temperature
ing. This problem was increasingly recorded at the outlet of the effluent con
reducing the availability of the hydroc
denser after the revamp is ranging
racker unit throughout the year, hence between 20--S0C, which is below the
reducing the refinery's ()verall gross mar
gin. Figure 2 shows the originallocation
coi.ps.~~rates/~~f -

of the effluent condenser.


Hydrocracker unit revamp
Banks
Train A
Train B
In light of the aboye, the hydrocracker
2S,3
A
21.7
was revamped in order to elimina te the
B
12.6
SO.6
persistent problem of HPNA formation in
e
84.3
8.4
the effluent condenser tubes . The
D
126
21
revamp comprised the following:
E
16.8
12.6
- The condenser was re-Iocated after the
F
10
16.8
high-pressure separator (HPS) which was
G
25.3
2S.3
then utilised as a hot separator
H
21.7
21.7
- The fractionator bottom, which was
directly sent to the first stage reactors,
was con verted into indirect recycle mode
rabie 2
by routing it to the vacuum column in
order to segrega te the HPNA material va
vel()dty- ~alcula~ins
distillation.
-Changing the effluent condenser orig
Size
Pre-revamp After revamp
inal design specification was not possi
Diameter,
Velocity,
Velocity,
ble. Therefore, the condenser retained
ineh
ft/see
ft/see
its original surface area and heat
(tu
bes)
12
1in
8
exchange-ability of 128.84 million
4in (outlet noules) 33
27
Btu/hr.
12in (inlet header) 26
21
However, the required heat duty after
16in
(outlet
header)
33
26
the revamp was 63.15 million Btu/hr. The
condenser mechanical design also
remained the same.
rabIe 3

47
PTQ WINTER 1999/ 1000

REFINING
crystallising temperature of the ammoni

um bi-sulphide salts. Moreover, the

exi'sling system is difficult to control

because the fans are fixed speed fixed

pitch. Therefore, precipitation of ammo

nium bi-sulphide in the effluent con

denser is always expected.

Hydraulic un-symmetry

The revamp contributed un-symmetrical

inlet piping to the ~ff1uent condenser,

which led to a faster corrosion rate due

to the change of hydraulic profile in the

system, as shown in Figure 4.

The piping un-syrnmetry caused flow


maIaistr6Utonro fhe condenser 5aks
leaaing to unbalanced ammonium bi-=
sulphide corrosion levels between the
ha nks.. This was evident when the con
denser was opened during the
tumarounds for inspection. Sorne of the
banks were experiencing severe ammoni
um bi-sulphide corrosion and sorne had a
moderate corrosion, as shown in Table 2.
These unbalanced corrosion rates are
primarily due to the uneven flow distri
bution among the condenser banks
along with the varying velocity ranges
from bank to bank.
W~jection malfunction
The wasb water un-s _metrical J~lRing
circuit t at resulted from-.J:he_.revamp
had greatly contributed to the ammoni
um bi-sulphide corrosion. As shown in
Fgure 5, it is obvious that water was
uneven~y distributed to the banks caus
ing the nearest banks to receive more
wash water than the farthest banks. As a
result, the farthest banks experienced a
higher ammonium bi-sulphide corrosion
rate than the n earest banks.
In addition to the wash water piping
circuit un-symmetry, the inadequate ]2er
formance and frequent failures of the
w~ection pumBs caused the water
injectlOn rate to be lower than the
design rate of 5-8 LV% oi fresh feed.
Along with that, tQ.e water had Ijgh.Q)q
gen content of about 1.6P.Q!!!,"which is
very1iigh compared to O.OSp;Im aL per
censor recommenda tions.
The high oxygen content was due to
the fact that wash water tanks were o]2en
to the atmosphere ~ithout nitrogen

I-"

Figure 5 Water injection malfunction

blanketing. Such high levels of oxygen


have beens hown to accelerate NH.(HS)
corrosion by 600 per cent in laboratory
experiments.

Inspection findings
In light of the aboye, Riyadh refinery
started its metaIlurgical analysis by tak
ing radiographic shots and applying
ultrasonic thickness measurements
which showed elevted metal loss rates
on the cond~ns~r tubesandpiRing cir
cuit ranging from 8-126 mils ;Ier y_e.ar
(refer Table 2) . In particular, the worst
corrosion rates occurred at the con
dser outIe"i noZzles. According to the
velocity calculations in Table 3, the 4in
outlet nozzles have the highest velocity
in the effluent condenser circuit. In
addition, the corrcsicn was founo
extremely localised~ t p()ints of high tur
bulence and high velocity.
Inspectionhistory
During an emergency shutdown in Jan
uary 1994, 13 four-inch outlet nozzles of
the hydrocracker effluent condenser

were renewed as a matter of urgency.


That was due to the drastic _thickness
reduction QL?~3.mm_aginst original
thiCkileSSof l~.lmm during_on~J:Ppnth
of o]2..'ation. Samples from the corrod-=
ed/eroded outIet nozzles were examinect
in the metaIlurgical laboratory. The sam
pie resuIts were as foIlows:
-Severe >itting of about 1.5mm ~eep
and iOcas-ed--i!o oving was noticed "at
the internal surface of the nozzles
- Localised grooving was noticed
between 3 to 8 o'dock positions ;t the
to;: portion of the nozzles
- Irregular shape of black mark at the
grains indicated grooving of the metal
internal surface
- Black microdots at the grain matrix
indicated pitting ::orrosion near the
i!ttemal surfaccs.
Tube cleaning history
In the 1989 turnaround, condenser
banks A, B, e and o from each train
were cleaned of the ammonium bi-sul
phide deposils. In the 1992 tumaround,
only banks G and H were deaned from

Corrosion rates, MPY

Banks

Train A

A
B

2.50
0.90
0.50
0.60
, .30
, .30
0.90
0.90

e
D
E
F

il

Table 4

Train B
0.60
3.0
0.50
0.30
. , .05
'040
0.30
, .90

Figwe

6 Symmetrical piping and single water injection


48
PTQ WINTER 1999/ 2000

REFINING
each train. From the aboye, it was founct that the ban..l<s were not
deaned ali at the same time, which fP..sulted in an uneven flow dis
tributio'n among the condenser banks. The high velodty causes ero
~ sion to the deaned bundles and low velodty causes Eouling to the
undeaned bundles. 11s practice has aggravated the piping un-sym
metry problem discussed aboye.
lt was concluded that the severe metal loss occurring in the
effluent condenser outlet nozzles was due to arnmonium bi-sul
phide corrosion and high outlet velodty, which intum leads to
erosion attack.

Remedial actions
The refinery carried out several remedial measures which were
intended to mitigate the ammonium bi-sulphide currosion prob
lem, thus ensuring the safety and integrity of the hydrocracking
unit. A total engineering solution of the subject eftluent con
denser arnmonium bi-sulphide corrosion \'Vas initiated and imple
mented as follows:
1. Nozzles alIoy overIay
The effluent condenser outlet nouJes were replaced in-kind with
~.1his was done to improve the resis
tance of the outlet nouJes to the high erosion/corrosion rates because
they maintain velodties of about 27ft/sec. Moreover, the lnconel 625
alioy nouJes can withstand a liquid velodty up to 3Oft/sec.
2. New water tanks and pumps
, . , A capital project was initiated to replace the ex.i.sting four water injec
tion pumps with three higher capadty and better type pumps. This
was done to ensure a delivery of 8 LV% water injection rateo Also,
new dosed water tanks with ~ alIevi
ate the oxygel),content in the water injection.
3. Piping symmetry

The effluent condenser iolet and outlet piping was made sym

metrical in order to ~~ among the con

denser banks. Moreover, the main outlet header diameter was

increased fri>m 16in to 18in to r~o~f!Q1P


27ft/sec to 22ft/sec, which is dose eno:.lgh to the normal range of

O=Zoftsec(Fg;:ue 6).

Water injection point


The wash water was originaliy designed to be injected into each indi
vidual bank with no measurements or control on the individual
water injection rates (Figure 5).
VVhen revamp took place, it furth~r created unbalanced Wl!ter dis
tribution to ali banks. Therefore, in an attempt to ensure perfect mix
between the wash water and the processed hot separator gas, a sin
gle water injection point was connected on the effluent condenser

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~(Figure6).

..Resultsand discussion
After the implementation oE the aboye actions, the current effluent
condenser operation signilicantly improved in terms of equal flow
distribution, even water wash distribution, and lower corrosion rates.
As shown in Table 4, the corrosion rates appredably decreased to
below the industrial norm of 3-5mpy after one year and a half oE
implementing the remedial measures. Also, no indications of high
fouling rate were discovered.
However, ammonium bi-sulphide corrosion is bound to occur
because of the unsolved <;ondenser temperature control problem.
Nevertheless, ali other ammonium bi-sulphide corrosion-influenc
ing factors are being optimised in order to compensate for the tem
perature control malfunction.

Coasta/ Cata/yst Techn%gy, Inc.


A SUBSIOIARY OF THE COASTAL CORPORA flON
The Energy Peaple

Send us your spent catalyst.

This article is based on a paper presented at the Asia Pacific Refining


Technology Conference, Singapore, 21-23 Aptil 1999.
Wald A A/-Naim is a hydrocracker engineer and simu/ation
specia/ist with Saudi Arameo, Kingdom of Saudi Arabia. He has
a 8ache/or's degree in chemica/ engineering from the University
of TU/50, Ok/ahoma, USA.

49
PTQ WINTER 1999/ 2000

IENQUIRY NO

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