KBR Advanced Ammonia Process (KAAP)

Commercial Applications
The KBR Advanced Ammonia Process (KAAP Process) flow sheet combines a conventional
reforming front end using KBR's proven Top-Fired Steam Methane Reformer (SMR) with KBR's
proprietary KAAP Ammonia Synthesis Loop.

Proven Process Technology

KAAP technology has been licensed for five commercially-successful grass roots ammonia plants
operating in Trinidad, each with a nameplate capacity of 1850 MTPD, A sixth KAAP plant with a
nameplate capacity of 2000 MTPD commissioned in Egypt the first quarter of 2009, and a seventh
1800 MTPD KAAP plant is under construction in Venezuela commissioned in 2010. The first two
grass roots KAAP ammonia plants in Trinidad have been operating successfully since 1998.

YEAR CLIENT LOCATION CAPACITY (MT/Day)

1998 PCS Nitrogen Trinidad 1850
1998 Point Lisas Nitrogen Ltd. Trinidad 1850
2002 Caribbean Nitrogen Co. Trinidad 1850
2004 Nitrogen 2000 Trinidad 1850
2008 EBIC Egypt 2000
2009 MHTL Trinidad 1850
2010 Pequiven Venezuela 1800

Values and Benefits

KAAP features ammonia synthesis over a proprietary promoted Ruthenium on graphite catalyst that
has an intrinsic activity ten to twenty times higher than conventional magnetite catalyst. This well-
proven catalyst allows efficient ammonia synthesis at only 90 bar syn loop pressure which is two-
third to one half the operating pressure required for conventional ammonia synthesis.

As a result of this low pressure, only a single-case synthesis gas compressor is needed and vessel
and pipe wall thicknesses are reduced throughout the synthesis loop, which reduces design
complexity and equipment costs.
KAAP RUTHENIUM CONVERTER
4-Bed Radial-flow Converter (GRASSROOTS)

The Grasroots ammonia plants typically utilize KAAP in conjunction with KRES, the Kellogg
Reforming Exchange System. Together, these processes have a multitude of benefits, several of
which stem from the sole implementation of KAAP. The lower pressure synthesis loop, which leads
to significant capital savings, results from the use of a single case gas compressor with thinner
walled and lighter vessels, fittings, and pipings. This synthesis loop is also advantageous in that it
uses energy more efficiently by recovering heat at a much higher temperature, yielding a 40%
decrease in energy conversion relative to conventional designs. Since the synthesis loop is less
complex than in other plants, operator attention is expected to be less as well. In addition, all of
these benefits bring with them an expectation of greater reliability.

The synthesis proceeds at about 90 bars in a 4-bed radial-flow converter (hot wall design) with inter-
bed exchangers. The first bed is charged with conventional iron-based catalyst for bulk conversion
and the other beds with Kelloggs high activity ruthenium-based catalyst, allowing to attain an exit
ammonia concentration in excess of 20%. The other process steps are more along the traditional
lines. The overall energy claimed for this process can be as low as 27.2 GJ/t NH3 (6.5 Gcal/t NH3).

ITEMS DESIGN ACTUAL

Production capacity (T/day) 1850 1918
Temperature rising of converter (dT/oC) 262 286
Ammonia concentration at outlet (mole%) 20 21.7
2-Bed Radial-flow Converter (RETROFIT)

The KAAP system was successfully started up in November of 1992. It consisted of a KAAP reactor
which was installed downstream from the magnetite converter already in existence. This KAAP
reactor was a two-bed radial flow converter with a unique proprietary sealing system which avoided
hot spots within the catalyst bed. The KAAP catalyst was loaded in its oxidized state, just as most
catalysts are, although it is only active in the reduced state. A continuous purge is required in this
retrofit because the expanded plant contains more inerts than in the original synloop. After the entire
KAAP retrofit was completed, PAI had an energy savings of 0.6 mmBTU/mt. This more efficient and
highly flexible system has been very easy to operate and has paved the way for grassroots facilities.

The two-bed, hot-wall KAAP reactor features a low pressure drop and radial flow. Because of the
KAAP catalyst's high activity, thin beds are necessary to keep operating temperatures within the
prescribed range.

Kellogg's reactor uses a proprietary sealing system. This

technology avoids the catalyst mal-distribution that can lead
to formation of hot spots in the catalyst bed. The system
also enables 100% of the loaded catalyst volume to be
utilized for reaction.

The stream enters the reactor through a side inlet and is

heated in the internal exchanger tubes. An external bypass
line around this exchanger provides first-bed inlet
temperature control.

The gas flows through the first bed, then on to the shell side
of the internal exchanger and to the second bed. The
effluent from the second bed of KAAP catalyst is about 19%
ammonia.

The effluent is cooled in a second medium-pressure steam

generator. It then flows to the shell side of the feed/effluent
exchanger (121-C).

Shell-side effluent from this exchanger is cooled in a water exchanger (124-C), where ammonia
condensation begins. A four-stage "unitized" exchanger completes the condensation process.

The ammonia is cooled to -33 C. in a two-case, centrifugal compressor. The refrigerated liquid is
then removed and sent to storage.
RUTHENIUM CATALYST - SIGNIFICANT FEATURES

In 1979, a novel catalyst for ammonia synthesis was prepared by loading carbonyl compound of
ruthenium on carbon containing graphite in laboratory. This kind of catalyst, with graphited carbon as
support and Ru3(CO)12 as precursor, possessed some special features that may be summarized as
follows:

1. High activity (more than 10-20 times than magnetite) and at high ammonia concentrations: Outlet
ammonia of reactor may be 20% - 21.7% at 91.4 kg/cm2.
2. Low temperature initiation, low pressure performance.
3. Expected catalyst life is the same as for magnetite, and is determined by loss of carbon support.
4. Poisons are the same as for magnetite and to approximately the same degree. Catalysts recover
after temporary poisons (H2O, O2, CO, CO2) are removed.
5. Like iron (magnetite) catalyst, dissociative adsorption of N2 is also the rate determining step on
ruthenium catalyst. The difference is that the absorption of H2 strongly inhibits the adsorption of
N2, while the inhibition effect for NH3 production is not apparent on ruthenium catalyst.
6. The latter is an advantage of ruthenium catalyst, so that the ruthenium catalyst can be placed
behind iron catalyst in synthesis ammonia process e.g. KAAP process.
7. When H2/N2 = 3, ruthenium catalyst exhibits the higher activity than the iron catalyst at high
temperatures. In addition, the situation is opposite with the increase of H2/N2 ratio. Thus,
ruthenium catalyst is suitable for use at low H2/N2.
8. Since ruthenium catalyst is expensive, highly active and readily inhibited by H 2, the process for
the ammonia synthesis must be modified to fit these features.