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Update catalyst technology

for syngas production

Changes in bed support maintain lower pressure drop across

shift reactor in ammonia processes
W. Khalid, Engro Chemicals Pakistan, Pakistan

ow pressure drop in the front end of an ammonia plant saves

energy needed to compress synthesis gas. Such operations
conditions can remove major processing bottlenecks when
increasing plant capacity. In this case history, a forced shutdown
enabled a catalyst retrofit reconfiguration of the media support
system. This decision improved unit operations and plant energy
efficiency.
Ammonia plant. Several processes are commercially available

to produce synthesis gas for ammonia (NH3) production. Steam/

air reforming of natural gas is the dominant processing method
used for NH3 synthesis. Fig. 1 is a simplified process flow diagram
of NH3 production.
Sulfur removal or feed gas purification. The first stage

of the NH3 process is the preliminary purification section, where

impurities, primarily sulfur compounds, are removed from the
gas stream. The desulfurization vessel contains a catalyst that
hydrogenates organic sulfur to hydrogen sulfide (H2S), which is
then absorbed in ZnO-based catalyst:

ZnO + H 2 S ZnS + H2 O
Sulfur and sulfur containing compounds
must be efficiently removed from the feed
gas to prevent poisoning of the nickel-based
reforming catalyst in the primary reformer
and other downstream catalysts. Chlorine,
if present in the feedstock, is also removed
via the feed purification section.

Process steam

C n Hm + nH2 O nCO + (n + m/2)H2

CO + H 2 O CO2 + H 2

In the secondary reformer, the necessary reaction heat is provided by internal combustion using air. The stiochiometric quantity of preheated process air is injected to introduce the required
nitrogen (N2) amount needed for NH3 synthesis.
Shift conversion section. Two-step shift conversion consists of
a high-temperature shift converter (HTSC) and a low-temperature
shift converter (LTSC). The reaction is:

CO + H 2 O CO2 + H 2
The performance of the carbon monoxide (CO) conversion section strongly impacts the total energy efficiency of the NH3 plant,
as unconverted CO will consume H2 and form methane (CH4) in
the downstream methanator, thereby reducing available H2 and
increasing the inert level/pressure within the synthesis loop.
CO2 removal and methanation section. The gas stream is
sent to the absorber column, where an activated hot potassium
Prereforming

Sec reforming

HT shift

LT shift

Feed purification
Natural gas
Process air

Reforming section. Steam reforming is

a well-established process for the manufacturing of hydrogen (H2) and synthesis gas.
This process is done in two steps namely
1) adiabatic pre-reforming, which allows
using of higher preheat temperature and
reduces the size of the primary reformer)
and 2) primary reformer. The reforming reaction(s) occurs place over a nickel
(Ni) catalyst loaded in vertical tubes. The
required reaction heat is supplied by combusting fuel gas. The endothermic steam
reforming reactions are:

CH 4 + H 2 O CO + 3H2

Primary reforming

WHB

WHB

Purge gas

Ammonia
product

CO2
CO2
removal

WHB
Ammonia synthesis
Methanation

Fig. 1

Process
condensate

Simplified NH3 process flow diagram. Source: www.topsoe.com.

HYDROCARBONPROCESSING april 2009

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SpecialReport

7 ft 10 in.

Sample
cages
6 ft 9 in.
6 ft
5 in.

Thermocouple
shaft
18 ft 9.5 in.

SK-202-2
1,500 ft3

Side man
way
MI

6 in. TI 126
3 in. 5%
6 in. TI 125
43.2%
3 in.

3 in.
6 in. TI 127
77.7%

5 ft 5 in.
Catalyst dumping nozzle

6 in.

22 in.

21 ft
23 ft 4 in.

in. AI balls, 100 ft3

in. AI balls, 100 ft3
in. AI balls, 450 ft3
Outlet nozzle

Fig. 2

Schematic details of previous catalyst loading.

Fig. 3

Visual of spent HTSC catalyst loading.

carbonate solution is used to absorb carbon dioxide (CO2) from

the gas, and NH3 sent to the stripper where it is regenerated and
the CO2 is stripped off with steam. The CO2 is forwarded along
with NH3 for urea production.
CO and CO2 are poisons to the NH3 synthesis catalyst and
must be removed (below 5 ppm) before the gas is fed to the synthesis section. This is achieved by converting the CO to CO2 in
the shift reaction and removing the CO2; finally, traces of CO2
and CO are converted back to CH4 in the methanator via these
reactions:
CO + 3H 2 CH 4 + H 2 O

CO2 + 4H 2 CH 4 + 2H 2 O
Syngas compression and synthesis sections. The gas is
cooled, and excess steam is condensed before the feed enters the
synthesis section. The compressed gas is pre-heated with hot
outlet gas from the ammonia converter. The exothermic reaction
takes place in a three-bed radial flow converter:

N 2 + 3H 2 2NH3
The formed NH3 is condensed and removed via a separator.
2

I april 2009 HYDROCARBONPROCESSING

24
22
20
18 142%
FEL
16
14
12

HTSC P from SOR

154% FEL
147%
FEL

152% FEL
147% FEL

153% FEL

18-Nov-02
16-Dec-02
20-Jan-03
24-Feb-03
17-Mar-03
17-Jun-03
25-Nov-03
03-Feb-04
02-Nov-04
08-Feb-05
16-Aug-05
11-Oct-05
13-Dec-05
14-Feb-06
14-Mar-06
13-Jun-06
29-Aug-06
26-Sep-06
31-Oct-06
19-Dec-06
09-Jan-07
20-Nov-07

22 ft

HTSC, P

Inlet nozzle

17 ft 1 in.
9 in.
rashing
rings

24 ft 7 in.

25 ft 10.5 in.

Perforated plate
vapor distributor

petrochemical developments

Date
Fig. 4

Pressure-drop profile of previous catalyst charge.

Initial catalyst and support media loading. The high-

temperature shift converter (HTSC) at the Engro Chemicals

Pakistan (ECPL) site is a cylindrical vessel with an inner diameter
of 16 ft. The loaded reactor holds 1,500 ft3 of catalyst. The vessel internals include a perforated plate vapor inlet distributor, an
elephant stool type outlet gas collector, a catalyst unloading nozzle
(protruding into the vessel) and a thermocouple shaft. The 22-in.
diameter inlet flange on top of the HTSC is used as a manway
for catalyst loading and a side manway can be used for catalyst
unloading. New catalyst was loaded in October 2002 (see Figs. 2
and 3) was at the end of catalysts service life:
Age
56 Months
Loaded volume of catalyst
1,500 ft3
Bottom inert support media
650 ft3
(-in., -in. and -in. alumina balls)
The start-of-run (SOR) pressure drop was 14 psi at front-end
load (FEL) of 142%. The pressure drop of the catalyst bed at
these initial conditions was only 3 psi, and the remainder was
contributed by 650 ft3 of the -in. and smaller sized alumina
balls loaded at the bottom as support media. Over time, the time
pressure drop increased to 24 psiend-of-run (EOR)due to
aging of catalyst.

This is going to be a callout. This is

going to be a callout. This is going to be a

callout. This is going to be a callout. This
is going to be a callout.
New loading scheme. Due to a forced plant outage from an

air compressor problem, ECPL engineers decided to replace the

HTSC charge. The plant loading had increased and, now with
154% FEL, the SOR pressure drop was estimated at 17 psi when
using the original catalyst loading scheme. This pressure drop was
expected to reach 25 psi by the end of catalyst service life.
The analysis of the loading pattern and the reactor drawings
revealed that elephant stool type outlet nozzle with smaller
size-alumina balls was the bottleneck. Also, the plant and current
loading pattern were of 1960s vintage design where pressure drop
and energy considerations were not so critical. The combination
of decreasing battery-limit pressure from feed gas supplies and

petrochemical developments
Inlet nozzle

8 ft 1 in.

Reclaimed
Sample
rashing rings cages

6 in.

2 in.
38 in.
Catalyst dumping nozzle

22 ft

Thermocouple
shaft

18 ft 9.5 in.
21 ft
23 ft 4 in.

16 ft 7 in.

Perforated plate
vapor distributor

3 in.
6 in. TI 126
5%

New catalyst
1,625 ft3
of SK-2001-2

6 in. TI 125
43.2%
3 in.

Side man way

3 in.
6 in. TI 127
77.7%

MI-22 in.

6 in.

Fig. 5

6 in.

22 in.

Outlet nozzle

in. AI balls
in. AI balls
1 in. AI balls
2 in. AI balls

Schematic details of new catalyst loading.

SpecialReport

previous loading pattern. This pressure drop is still consistent after

more than a year of service. Also, due to the forced outage, the
project was done earlier and savings started a year ahead of plans.
By calculating the savings in terms of steam used by the synthesis
compressor, the retrofit savings are approximately $600,000/yr
for this part of the world.
Deferring gas-booster compressor revamp. Due to the 17 psi
total margin before and after loading, the retrofit project for the
feed-gas booster compressor was deferred and will be rescheduled
with planned outage.
Low CO slip and higher production. After five years of
operation, CO slip had increased to 3.2% at th HTSC outlet.
Presently, at slightly higher load and lower steam to gas ratio, the
CO slip is 2.2%. Result: Lower inerts present in the back-end
synthesis loop. This, coupled with high suction pressure at the
synthesis compressor (due to lower front-end presser drop) enables
more NH3 production. HP

Waskim Khalid is the head of process engineering in Engro

Chemical Pakistan Ltd. He holds a degree in chemical engineering
from University of Engineering and Technology, Lahore in 1995.
Since then, he has gained experience in design, capacity enhancement, modification, performance monitoring and optimization of
different fertilizer and oil and gas facilities. Also, Mr. Khalid has worked as a lead
process design engineer in a large multinational EPC company.

Fig. 6

Visual of new HTSC catalyst loading.

limitations from the gas-booster compressor had limited processing capacity and NH3 production.
At this point, ECPL engineers decided to modify the loading pattern of alumina balls by fabricating new mesh support
and installing larger sized alumina balls. The alumina balls were
arranged locally during the outage. In the new loading pattern,
instead of using -in., -in. and -in. , larger sized (2-in. and
1-in.) alumina balls were loaded at bottom portion. To limit catalyst pellets penetrating to outlet distributor mesh, in. alumina
balls and a small quantity of in. balls were loaded as a top layer
for the support media (see Figs. 5 and 6):
New loaded catalyst volume
1,625 ft3
2-in. alumina balls
50 ft3

(limited by availability)
1-in. alumina balls
100 ft3
-in. alumina balls reclaimed
350 ft3
-in. alumina balls reclaimed
100 ft3
Advantages with new loading scheme. With this new

design, several major advantages were realized immediately:

Pressure drop. The results were very encouraging; and pressure drop is only 7 psi at full load vs. the envisaged at 17 psi for

HYDROCARBONPROCESSING april 2009

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