Effect of reactor inlet temperature

in a hydrotreater
Solving a problem of pressure drop in a naphtha hydrotreater led to fresh
insights into the role of reactor inlet temperature

AMIT KALYAN CHANDRA

Indian Oil Corporation Limited

I
n a petroleum refinery, a cat-
alytic reforming unit (CRU) is
set up to increase the octane Low COT Stripper
number of naphtha through offgas

reforming reactions. A CRU is First Second

always accompanied by a naph- reactor reactor

tha hydrotreater unit (NHDT)

High Normal Reflux
∆P ∆P pump
tasked with preparing the feed, Recycle gas
compressor
primarily to remove sulphur
from naphtha feed as sulphur Stripper
Feed column
acts as a poison for CRU cata- heater
Low reactor
effluent temp.
Make-up
lyst. A process flow diagram hydrogen

of a typical NHDT is shown in

Recycle gas
Feed/effluent rich in
heat exchanger hydrogen
Figure 1.

Process description Reboiler

The process can be broadly cat-
egorised into a high pressure
reaction section (the HP sec-
tion) and a low pressure strip-
per section (the LP section).
High pressure reaction section
The naphtha feed (90-140 cut)
mixed with recycle gas, pre-
dominantly hydrogen, is
heated in a series of feed efflu-
ent exchangers before being fed
to the fired heater where the
feed mixture is heated to the
required reaction temperature.
There are two reactors
arranged in series where the
feed mixture undergoes an exo-
thermic hydrodesulphurisation
furnace
Feed High pressure
Naphtha pump separator
storage tank Desulphurised
naphtha to CRU
Figure 1 Process flow diagram of a naphtha hydrotreater unit
reaction to yield desulphur- cled to recycle gas compressor
ised naphtha and hydrogen sul- suction and partly purged to
phide (H2S): the refinery fuel gas header.
Low pressure stripper section
R-SH + H2 = R-H +H2S (1)
The liquid stream from the sep-
arator bottom, rich in dissolved
The reactor effluents are fed H2S, is fed to a stripper col-
to a high pressure separator. umn where the H2S is stripped
The vapour stream from the out. The stripper bottom des-
separator top mainly consti- ulphurised naphtha is fur-
tutes unreacted hydrogen. The ther processed in the catalytic
vapour stream is partly recy- reforming unit.

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First reactor ∆P, kg/cm2
Figure 2 Differential pressure drop across the NHDT first reactor catalyst bed
Problem faced
In the present case, the pressure
drop across the NHDT first
reactor would increase sharply
after the plant was operated for
a few months (see Figure 2).
This increased pressure drop
would hamper normal unit
operation. It was a recurring
problem and the unit had to be
shut down to unload and skim
the catalyst.
Suspected reasons for pressure
drop
Gum formation
Often the reason for pressure
drop in a naphtha hydrotreater
is attributed to the tendency of
olefins to react with oxygen to
form gum. In the present case,
the gum formation theory was
discarded because: no cracked
feed was processed and hence
the olefin percentage of the feed
was minimal; and a floating
roof feed tank was being used,
so there was no opportunity for
reaction with oxygen.
Foreign particles
It was suspected that foreign
particles might have deposited
on the catalyst bed, plugging the
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6
5
0
1 21 41 61 81 101 121 141 161 181 201
Time, days
void spaces and increasing the
pressure drop across the bed.
These particles could be gener-
ated as a result of erosion/corro-
sion in connecting pipelines and
the feed storage tank.
Surprisingly, no such pres-
sure drop was observed across
the magnetic filter (which is
supposed to trap such particles)
in the feed line. Even down-
stream of the filter, no line thin-
ning of connecting pipelines
(that would have suggested
corrosion) was observed, thus
discarding the theory of foreign
particles plugging the catalyst
bed.
Coke formation
It was suspected that cok-
ing might be responsible for
increased pressure drop across
the catalyst bed. On opening
the reactor bed during catalyst
unloading and skimming, car-
bon deposits were found on the
catalyst, so supporting the the-
ory of coking.
However, the following
factors argued against this
analysis:
• The feed used was straight
run naphtha (90-140 cut)
221 241 261 281 301
• The reaction temperature was
only 290°C
• The reaction was taking
place in the gaseous phase in a
hydrogen atmosphere.
Thus there was no explana-
tion as to how the feed naphtha
could be cracking at a temper-
ature of 290°C in a gaseous
phase reaction carried out in a
hydrogen atmosphere and yet
generating coke.
More evidence further con-
tradicted the coke formation
hypothesis. In previous runs,
the NHDT reaction tempera-
ture was maintained at 315°C,
but the problem of increased
pressure drop across the reactor
was not encountered.
The catalyst of the NHDT
unit had been changed and the
new catalyst required reduc-
tion of the NHDT reaction tem-
perature to 290°C. The new
catalyst’s guidelines pointed
out that increasing the reac-
tion temperature can lead to a
recombination reaction (mer-
captan recombination), which
would affect the quality of the
product:
R-H +H2S = RSH + H2 (2)
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 240

Feed preheat temperature, ºC 230

220

210

200

190
High feed preheat
Low feed preheat
180
1 21 41 61 81 101 121 141 161 181 201 221 241 261 281 301
Time, days

Figure 3 Feed preheat temperature for two cases

Reduction of the reaction moted by an increase in tem- reactor at a reduced reaction

temperature was a welcome perature. However, it was not temperature?
change as it offloaded the clear why, when the reactor The heat of the reactor efflu-
NHDT fired heater. Even at a was being operated at a higher ents was being utilised to pre-
reaction temperature of 290°C, reaction temperature, there was heat the unit feed to heater
the naphtha feed was being no coking, but when the reac- inlet temperature. In the pres-
desulphurised as was evident tion temperature was reduced ent case, the reaction tempera-
from the CRU feed that always keeping all other parameters ture was reduced from 315°C
tested positive for less than 0.5 identical, substantial coke dep- to 290°C. This substantially
ppm sulphur. osition was detected in the reduced the reactor effluent
Cracking, often held respon- reactor. temperature. Hence, the feed
sible for coking and being an So what might have triggered preheat was also substantially
endothermic reaction, is pro- coke deposition in the NHDT reduced by 15-25°C.

5.0
Catalyst bed ∆P, kg/cm2

4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
1 21 41 61 81 101 121 141 161 181 201 221 241 261 281 301
Time, days

Figure 4 Differential pressure drop across the catalyst bed with high feed preheat

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 6
Low feed preheat
5 High feed preheat
4
∆P, kg/cm2
0
1 21 41
Figure 5 Differential pressure drop across the catalyst bed for two cases
The fired heater has been
designed to handle vapour feed
but, as a result of the reduc-
tion in feed preheat, the heater
was forced to accept mixed feed
(vapour and liquid). The liq-
uid, once exposed to high heat
flux on entering the fired heater
tubes, cracked, forming coke.
The coke formed was entrained
with the feed to the reactor,
blocking the reactor bed and
increasing pressure drop across
the bed.
Remedial action
The NHDT reaction temper-
ature was increased to 315°C.
This simultaneously increased
the feed preheat, resulting in a
fully vaporised feed being fed
to the fired heater. The feed
preheat temperatures have
been plotted for both cases (see
Figure 3).
The increasing rate of pres-
sure drop across the NHDT
reactor was regulated (see
Figure 4).
In support of this remedial
action, the pressure drop across
the catalyst bed has been plot-
ted for two different cases, one
with feed preheat in the range
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61 81 101 121 141 161 181 201
Time, days
210-215°C, the other with feed
preheat in the range 225-230°C
(see Figure 5).
From the plot, it can be
clearly inferred that the rate
of rise in differential pressure
drop with low feed preheat was
0.5 kg/cm2/month and that
with high feed preheat this was
0.01 kg/cm2/month.
Two important points can be
inferred from this case study.
Reaction temperature is popu-
larly believed to affect the rate
and conversion of reactions.
In the present case, lowering
the reaction temperature did
not lower the conversion rate.
However, lowering the reaction
temperature reduced the feed
preheat which in turn adversely
affected the unit, being respon-
sible for coke deposition in the
catalyst bed.
Conclusion
In a typical NHDT unit, the
pressure drop across the hydro-
treater reactor was increasing at
a sharp rate, rendering it almost
impossible to maintain normal
unit operations. The unit had
to be shut down to unload and
skim the catalyst.
221 241 261 281 301
Coke deposition on the cata-
lyst bed was detected and iden-
tified as the culprit behind a
high pressure drop across the
hydrotreater reactor. The unit
was being operated at a lower
reaction temperature than
used to be maintained in pre-
vious runs when no such prob-
lem of coking was faced. It was
unclear what might have led to
coke deposition on the catalyst
bed.
It was observed that reducing
reaction temperature did not
affect the conversion rate, and
the quality of product was not
compromised, but it did have
an adverse effect on the unit
operation. Reducing the reac-
tion temperature subsequently
reduced the reactor effluent
temperature. The heat of the
reactor effluent was in turn
being used to preheat the feed.
As a result, preheat was sub-
stantially reduced.
The NHDT fired heater had
been designed to handle fully
vaporised feed. In this case, it
was being fed with mixed feed.
The liquid part of the feed,
when exposed to high heat flux
in the heater, cracked, leading
www.digitalrefining.com/article/1001546
to coke formation in the heater
tubes. This coke, when carried
to the reactor bed, plugged the
void spaces and increased the
pressure drop across the reac-
tor bed.
Increasing the reaction tem-
perature regulated the rate of
increase in the pressure drop
across the reactor bed and the
problem was solved. The pres-
ent case study revealed that
reactor inlet temperature not
www.digitalrefining.com/article/1001546
only affects the rate and con-
version of reactions, it also
plays a critical role in affecting
pressure drop across the reac-
tor bed.
Amit Kalyan Chandra is an Assistant
Manager with Indian Oil Corporation
Limited. With more than five years
of operational experience in crude
distillation, naphtha hydrotreating,
catalytic reforming and kero-
hydrodesulphurisation, he holds a
bachelor of chemical engineering degree
from Jadavpur University and is an
Associate Member of the Indian Institute
of Chemical Engineers and the Institution
of Chemical Engineers.
LINKS
More articles from the following
categories:
Fired Heaters, Furnaces and
Boilers
Catalysts and Additives
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