Urea Product Expansion by Newly

Developed CO2 Recovery Process from

Primary Reformer Flue Gas
Urea production of 110% has been expanded by the newly developed CO2 recovery process from
Primary Reformer flue gas in ammonia plant.
Kansai Electric Power Co. INC. and Mitsubishi Heavy Industries, Ltd. have been collaborating on the
development of the flue gas recovery technology since 1990. The first commercial plant for flue gas
CO2 recovery using the newly developed solvent (KS-1) has been operating commercially in Malaysia
since October 1999. KS-1 solvent has been developed for low partial pressure of carbon dioxide such
as the flue gas of the primary reformer, auxiliary boiler, gas turbine and so on.
In the Malaysian ammonia and urea complex plant, ammonia production was not balanced with CO2
production due to the natural gas source with the rich methane. Therefore, the urea production was
limited by the shortage of CO2 production and the excess ammonia was accumulated in the storage
tank or purge gas and the excess syn-gas was fired as reformer fuel. Petronas Fertilizer (KEDAH)
SDN. BHD. Company had decided to install the newly developed CO2 recovery system from the
reformer flue gas to increase the urea production and to balance the ammonia production with the CO2
production, increasing urea capacity from 1800 MTPD to over 2000 MTPD.
By applying this new technology, it is possible to match the ammonia production with CO2 production
for the full conversion to the granule urea product with recovery of the carbon dioxide from the flue
gas independent of the natural gas source that is supplied. As a result, the heavier components of
ethane, propane, butane will be extracted from the natural gas source at the upstream plant and the
extracted gas will be used separately for the ethylene plants and propane supply, with the remaining
natural gas containing the rich methane being supplied to the fertilizer and methanol plants.
This new technology will reduce the effluent CO2 in the flue gas from the primary reformer and help
the Kyoto Protocol for reducing CO2 effluent gas.
Ryota Shimura
Mitsubishi Heavy Industries, LTD
Co-Author : Petronas Fertilizer (Kedah) Sdn Bhd
feed. It is expected that the trend of using natural
gas for the ammonia and methanol plants will
steadily increase.

Introduction

N
2006

atural gas has been the primary feed

source of the synthesis gas in ammonia
and methanol plants opposed to naphtha

Usually ammonia produced in an ammonia plant is

237

AMMONIA TECHNICAL MANUAL

converted to granular urea with the carbon dioxide

which is also produced in the ammonia plant.

However, it is not feasible to install ammonia

export facilities such as the ammonia loading or
the ammonia storage bottling because of the small
quantity of the excess ammonia production.

In case of using the natural gas feed source in the

ammonia and urea complex plant, an excess of
ammonia is normally produced since more
ammonia is produced than carbon dioxide.

Therefore, the purge gas extracted from the

synthesis loop is sent to the ammonia recovery
unit and only ammonia is recovered from the
purge gas and the remaining purge gas including
methane, nitrogen and extensive quantities of
hydrogen is used for the reformer fuel in order to
treat the excess hydrogen.

Therefore, the reformed hydrogen gas from the

ammonia plant is used for the primary reformer
fuel to prevent the excess ammonia production in
natural gas feed plant. The excess ammonia can be
converted to urea product if CO2 gas is imported
from the outside.

In case that excess ammonia is still being

produced even when the purge gas including
hydrogen is used for the reformer fuel, the excess
synthesis gas is withdrawn from the outlet of
methanator and then fired in the reformer with the
purge gas until the CO2 product is matched with
the ammonia product for the urea plant.

In this paper, it is mentioned that the urea

production can be enhanced by the recovered CO2
from the primary reformer flue gas of the ammonia
plant using natural gas as feed source.
The new developed CO2 recovery solvent (KS-1)
is suitable for recovering the CO2 gas from the
reformer flue gas.

This results in the front end facilities such as

primary, secondary reformer, reactors, waste heat
facilities and CO2 removal facilities increasing in
capacity compared to the synthesis loop facilities
and also the higher energy consumption due to
firing the hydrogen reformed from natural gas.

Conventional Ammonia Plant

In an ammonia plant using natural gas feed, an
excess of ammonia is normally produced since the
hydrogen is produced more than the carbon dioxide
due to the methane rich in natural gas.

CO2
NH3
Tank
NG

HDS

Reforming
(Primary/2ndary)

HTS/
LTS

CO2
Removal

Methanator

NH3
Synthesis

Compression

NH3

Urea
Plant

ARU

Syn Gas Purge for Fuel H2/CH4/N2

Refrigeration

Urea

Purge Gas H2/CH4/N2

ARU: Ammonia Recovery Unit

Figure 1. Conventional Ammonia Plant

AMMONIA TECHNICAL MANUAL

238

2006

In addition, the product ammonia is stored in

ammonia storage tank during stoppage of urea
plant. It is difficult to convert the stored ammonia
in the tank to urea product in normal operating
condition because of the lack of CO2.

plant by the chemical absorption and the recovered

CO2 gas and excess ammonia is converted to urea
product.
However, the conventional solvent is not suitable
for absorbing the CO2 gas from the flue gas in the
primary reformer due to the low partial pressure of
CO2 in flue gas and the high energy consumption
for the CO2 regeneration.

In order to convert the ammonia in the ammonia

storage tank to urea product, it is required to
reduce the synthesis loop load with the normal
front end operation and vent the excess syn-gas to
flare upstream of the synthesis loop in order to
produce the necessary CO2 gas. (See Figure-1)

Also, the degradation of amine in the CO2

recovery system, higher amine consumption and
corrosion trouble have been reported using
conventional solvent like mono-ethanolamine.

Advanced Ammonia and Urea Complex

Plant with Flue Gas CO2 Recovery

Therefore, it is necessary to develop the new

solvent for recovering the CO2 gas in the reformer
flue gas. It is found that the new CO2 recovery
solvent (KS-1) developed by Kansai Electric
Power Company and Mitsubishi Heavy Industries,
Ltd. is suitable for recovering CO2 gas from the
reformer flue gas.

The excess ammonia can be converted to urea

product by importing CO2 gas from the outside of
plant and the hydrogen gas from the synthesis
purge gas can be recycled to the suction of the
syn-gas compressor. However, it is very rare to
have a CO2 gas supply plant near the ammonia and
urea complex plant.

The flow scheme of the advanced ammonia and

urea complex plant with the CO2 recovery process
from the flue gas in the primary reformer is shown
in Figure-2. This new developed scheme solves
the problem of the shortfall of CO2 gas and the
excess ammonia production.

It is considered that CO2 gas is extracted from the

flue gas of the primary reformer in ammonia

CO2

CO2 Recovery
(KS-1)

CO2

Reformer
Flue Gas
NG

HDS

Reforming
(Primary/2ndary)

NH3
Tank

CO2
HTS/
LTS

CO2
Removal

Methanator

Compression

NH3
Synthesis

NH3

Urea
Plant

ARU
Urea

Refrigeration
Recycle H2

Purge Gas CH4/N2

HGRU

ARU: Ammonia Recovery Unit

HGRU: Hydrogen Recovery Unit

Figure 2. Advanced Ammonia & Urea Complex Plant with Flue Gas CO2 Recovery

2006

239

AMMONIA TECHNICAL MANUAL

exhaust gas. This new developed solvent is being

named KS-1 solvent.

New CO2 Recovery System

CO2 absorption from the boiler flue gas or the gas
turbine exhaust gas in the power plants by the
chemical absorption methods requires the high
energy for the regeneration of the absorbents
containing CO2 because of the low partial
pressure of CO2 in the flue gas.

The MHI advanced CO2 removal system offers

comprehensive advancements in process
configuration and energy efficiencies over
conventional systems.
Extracted flue gas is cooled down from 200 degC
to 40-50 degC through the flue gas cooler and the
exhaust cooled gas flows to the CO2 absorber and
the CO2 gas in the flue gas is absorbed by KS-1
solvent in the CO2 absorber while the remaining
gas is exhausted from the top of the CO2 absorber
to atmosphere.

Kansai Electric Power Company and Mitsubishi

Heavy Industries, Ltd. have been collaborating on
the development of flue gas CO2 recovery
technology since 1990 which is named Kansai
Mitsubishi Carbon Dioxide Recovery (KMCDR)
process.
A comprehensive range of available amines were
examined and tested, with the new advanced
KS-1 solvent developed without toxic,
dramatically improving CO2 absorbency,
regeneration and low degradability.

KS-1 solution absorbing CO2 is pumped up to the

CO2 regenerator and CO2 is regenerated by the
steam reboiler at the bottom of the regenerator.
The regenerated CO2 product gas is cooled down
at the overhead cooler at the top of regenerator
flowing to the user such as urea plant, methanol
plant and CO2 gas plant. (See Figure -3)

This CO2 recovery system is suitable for

absorbing the low partial pressure of CO2 gas
such as the boiler flue gas and the gas turbine
Flue Gas
to Atmosphere

CO2
Purity : 99.9 %

ABSORBER

STRIPPER

C.W.

C.W.

Flue Gas
Cooler

C.W.
Flue Gas
Reboiler

C.W.

Steam

Figure 3. Flue Gas CO2 Recovery System

AMMONIA TECHNICAL MANUAL

240

2006

Application of CO2 Recovery Process

from Flue Gas to Ammonia & Urea
Complex Plant

primary reformer.

Recently, it is requested to study that the source of

the ammonia and urea complex plant is changed
from naphtha to natural gas feed to improve the
energy consumption by the owner of the fertilizer
plant and a few projects have reached engineering
stage.

The natural gas condition is similar to the gas

source supplied from the liquid natural gas plant.

The study result of both cases is shown as follows.

Natural gas source:

CH4: 98%, C2H6: 1%, C3H8: 0.5%, N2: 0.5%
Production:
Ammonia 1350 MTPD, Urea 2380 MTPD

In this study using the natural gas feed, the

excess ammonia will be produced because of the
lack of CO2 production.

CO2 gas is needed to 1750 MTPD for the full

conversion of the ammonia product to urea plant
including the CO2 gas loss in urea plant.

A conventional counter measure of CO2 gas

shortfall is that excess natural gas is reformed in
the primary reformer in order to produce CO2 gas
matched with the urea production as described
the above.

The above natural gas leads the lack of CO2

because of methane rich in the natural gas. Which
means excess hydrogen is produced from the
natural gas for the necessity of CO2 gas and is used
as the primary reformer fuel. (See Figure-4).

Alternative way is that the necessary CO2 gas for

urea production is recovered from the flue gas of

CO2: 1770 MTPD

NG

HDS

CH4: 98%

Reforming
(Primary/2ndary)

HTS/
LTS

CO2
Removal

Methanator

Compression

NH3
Synthesis

NH3:
1350 MTPD

Urea
Plant

ARU

Syn Gas Purge for Fuel H2/CH4/N2

Refrigeration

Urea:
2380 MTPD

Purge Gas H2/CH4/N2

Capacity Increase : Front-End (HDS to Methanator) 1490 MTPD NH3 = 110% of 1350 MTPD
Back-End (Compression to NH3 Synthesis & Refrigeration) 1350 MTPD

ARU: Ammonia Recovery Unit

Figure 4. Larger Front-End Capacity Case

Alternatively in case of installation of the new
CO2 recovery system at the reformer stack, the
necessary CO2 gas of 160 MTPD is extracted from
the flue gas in the primary reformer.

the source of the urea product. As a result, it is not

necessary to fire the excess syn-gas in the reformer
and the hydrogen in the purge gas is recovered by
the additional hydrogen recovery unit at the outlet
of the ammonia recovery unit and the recovered
hydrogen is recycled by the suction of the syn-gas
compressor. (See Figure-5)

The CO2 gas is mixed with the other CO2 gas from
ammonia plant and the mixed CO2 gas is used as

2006

241

AMMONIA TECHNICAL MANUAL

The new flue gas CO2 recovery system reduces the

consumption of the process natural gas by 10 %. It
means that the front-end facilities such as primary
and secondary reformer, reactors, the waste heat
facilities and CO2 removal facilities can be
reduced to 90% or the ammonia and urea
production can increase to 110% if the ammonia
synthesis system and urea & granulation plant
have enough margin.

Gcal/MT-NH3 (LHV Base) because of reducing the

consumption of process natural gas dramatically.
(See Table-1)
In addition, if this CO2 recovery plant is installed
in a methanol plant, the extracted CO2 from the
flue gas in the steam reformer is mixed to process
natural gas or the synthesis gas and then methanol
production can increases to 110 120% because
CO and CO2 gas is the source of the methanol.
The unit operations energy consumption is the
same as the original methanol plant even though
the utility consumption of CO2 recovery system
and the CO2 booster compressor is considered.

Considering the utility consumption in the flue gas

CO2 recovery plant such as the electricity of the
flue gas blower, additional cooling water and the
regeneration steam, the total unit energy
consumption of ammonia plant reduces by -0.11

CO2 Recovery
(KS-1)

CO2: 160 MTPD

CO2: 1770 MTPD

Reformer
Flue Gas
NG

HDS

CO2: 1610 MTPD

Reforming
(Primary/2ndary)

HTS/
LTS

CO2
Removal

Methanator

NH3
Synthesis

Compression

NH3:
1350 MTPD

Urea
Plant

ARU

CH4: 98%
Refrigeration
Recycle H2

Purge Gas CH4/N2

Urea:
2380 MTPD
HGRU

Additional CO2 Recovery Unit (160 MTPD) & HGRU

(Purge Gas Recovery Unit) for 1350 MTPD NH3

ARU: Ammonia Recovery Unit

HGRU: Hydrogen Recovery Unit

Figure 5. Flue Gas CO2 Recovery Case

Table 1. Comparison of Energy Consumption
[Gcal/MT-NH3]
Process NG
Fuel NG
Export Steam
Total

AMMONIA TECHNICAL MANUAL

Larger Front-End
Base
Base
Base
Base

242

CO2 Recovery
0.549
+ 0.316
+ 0.124
0.109

2006

by suction of the CO2 Compressor in the urea plant

and then it is used for the source of the granule urea.

First Commercial CO2 Recovery Plant

The first commercial flue gas CO2 recovery plant
using KS-1 solvent for the ammonia and urea
complex plant has been constructed in Petronas
Fertilizer (Kedah) Sdn Bhd in Malaysia.

This CO2 recovery plant leads the urea product

expansion from 1800 MTPD to 2000 MTPD. The
flue gas CO2 recovery plant started on 20th
October, 1999 and has operated continuously.
Excellent performance of the process in terms of
low steam consumption, very low solvent loss has
been confirmed comparing the conventional
solvent.

Petronas Fertilizer (Kedah) Sdn Bhd (PFK) has a

complex for ammonia (1350 MTPD), urea (1750
MTPD), methanol (200 MTPD) and urea
formaldehyde (17 MTPD) at Kedah in Malaysia.
This plant has urea bagging and handling
facilities and also ammonia export facilities
including ammonia bottling, truck loading and
rail loading. Therefore, the excess ammonia can
be treated through these export facilities.

Main operation parameters of the flue gas CO2

recovery plant are as follows;
- CO2 Purity......................More than 99.9 vol% (Dry
base). Impurities are nitrogen and oxygen
- CO2 Recovery Ratio ......90 % at normal operation,
however more than 97 %CO2 recovery was
attained by increasing steam consumption
- Steam Consumption.......1.5 ton low pressure steam
(@3.5K/G) / ton CO2 recovered
- Amine Loss....................0.35 kg/ton CO2 Recovered
(See Figure -6, Table-2 and Table-3)

At first, PFK designed larger front-end facility in

the ammonia plant in order to produce CO2 gas
matched with the ammonia production in case of
supplying methane rich gas.
Moreover, considering the risk of stopping the
ammonia export facilities by the unexpected plant
stoppages in future, PFK continued to study the
way of the treatment of the excess ammonia in the
unexpected accidental conditions and finally
decided not only to increase the front-end
capacity but also to install the new CO2 removal
system which extracts 160 MTPD (Max. 200
MTPD) CO2 gas from the primary reformer flue
gas in ammonia plant.

Table 2. Design Conditions of Flue Gas

CO2 Recovery Plant
- Flue Gas Source
Steam Reformer Flue Gas
- Flue Gas Flow Rate 47,000 Nm3/H
- Flue Gas Temperature 168C
- Flue Gas Composition
(vol.%)
N2
67.79
8.08
CO2
O2
0.85
Ar
1.00
22.28
H2O
SOx
2.44(ppm)
NOx
200 (ppm)
Total
100.00
- CO2 Recovery %
90%

In addition, PFK also made the decision of

designing enough margin of the urea and
granulation capacity considering the additional
facility of CO2 recovery system. This CO2
recovery system leads to the full conversion of
ammonia product to urea product and can treat the
stored ammonia in the ammonia storage tank in
any operating case. As a result, operating
flexibility increases significantly in this plant.
In the PFK plant, CO2 gas recovered from the flue
gas of the steam reformer in the ammonia plant is
mixed with the other CO2 product from the
Benfield system in the ammonia plant and delivered

2006

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AMMONIA TECHNICAL MANUAL

the urea production with natural gas as source.

Table 3. Product CO2 Condition

This system can also recover the necessary CO2

gas for treating the stored ammonia in the storage
tank from the reformer flue gas. Which means the
excess urea product can be produced from the
stored ammonia in normal operating condition if
the urea and granulation plant has excess margin.

3,400 Nm3/H
(160 MTPD)
Max. 200 MTPD
- Recovered CO2 Pressure 0.55Bar Gauge
- CO2 Purity
More than 99.9 vol.%
(Dry Base)

- CO2 Flow Rate

This advanced system has been operating at

Petronus Fertilizer in Malaysia since 1999 and in
Japan for CO2 product from 2005.
Two expansion urea projects are at construction
stage in India and one expansion urea project is at
engineering stage in Middle East with another at
feasibility study stage with results highlighting
considerable expansion potential for methanol
gross.
The application of the new CO2 recovery system
to the EOR (enhanced oil recovery) are also being
studied, where the recovered CO2 gas from the
power plant is injected in the oil field to increase
the oil production.
In the future, it will be expected that the useful
ethane, propane and butane are extracted from the
natural gas at the well of natural gas and they are
supplied to the ethylene plant, chemical plant, and
propane gas plant with remaining natural gas
containing rich methane is supplied to the
fertilizer and methanol plant. At this time, this
newly developed CO2 recovery system helps the
fertilizer and methanol plants. (See Figure-7)
In addition, this advanced technology can reduce
effluent CO2 gas to 90% in the flue gas from the
primary reformer in ammonia and methanol plant
and helps the Kyoto Protocol for reducing CO2
effluent gas.

Figure 6. CO2 Recovery Plant

in Petronas Fertilizer (Keda) Sdn. Bhd.
Conclusion
This advanced developed CO2 recovery system
helps to a balance of the ammonia production and

AMMONIA TECHNICAL MANUAL

244

2006

CH4

Natural Gas

Ethane &
Propane
Recovery
Plant

C2

C1, C2, C3, C4+

C3

C4+

Fertilizer &
Methanol Plant
Ethylene Plant

Chemical & Gas Plant

Heavier

Figure 7. Natural Gas Distribution

References

Mimura, T., Satsumi, S., Iijima, M. and

Mitsuoka et al. (1999) Proceedings of the Fourth
International Conference on Greenhouse Gas
Control Technologies, Interlaken, Switzerland,
(Editors: Reimer, P, Eliasson, B. and Wokaun,
A.), Pergamon, p.71

Mimura, T., et al (1995) Energy Covers, Mgmt 36

(1995) p.397
Mimura, T., et al. 1996, Carbon Dioxide Removal,
Cambridge, MA, USA. 9-11 September 1996, p.57

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