New generation purification

catalyst technology
PRASANTH KUMAR, NORBERT RINGER
Clariant Middle East
Manama, Bahrain

Over the years, the severity of Synthesis Gas plants including Ammonia increased many
fold in certain locations on account of increased severity of operation, processing more dirty
feeds coming from deeper wells mostly containing (un)known poisons. One of the reasons for
this is because drilling companies switched over to newer wells (older wells for ex. more than
20 years in certain locations were abandoned) suddenly causing presence of unknown
poisons. While this feed switch over occurred, there was no change in purification catalyst’s
(amount and types) installed. Even though there was improvement in terms of increase in
activity and selectivity of various catalysts involved in syn gas plants, these were not used for
these ever demanding locations. In fewer plants while Process department monitored most of
the catalyst sections, Purification train was considered as simpler piece of operation and
managed by Utilities department and many times over looked.
Most types of poisons present in hydrocarbon feed stock of an Ammonia / Hydrogen / Oxo
Alcohol and Methanol plants are Sulphur, Chlorine, Lead ,Arsenic and Mercury. The effects of
these, as single or combined are different and depend upon many factors including the feed
type, composition, poison concentration and type.
In addition to the industry standard brand names such as “ReforMax® series”, “Shift Max®
series” and “AmoMax-10” catalyst series, Clariant has a variety of purification catalyst
portfolio under the brand name “ActISorb® series” series. This is used for various purification
application such as “Mercury Guard”, “Arsenic Guard”, “Sulfur Guard “ ,“Chloride Guard”,“
Silica Guard” and “Metal Guard”.
This paper covers various cases experienced by Ammonia / Methanol plant in MEA on
account of variety of poisons that can potentially affect the Reformer and LT Shift catalyst and
how they could save costly downstream catalyst failure and plant shut down by using state of
art purification catalyst from the Clariant’s catalyst portfolio.

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INTRODUCTION
We are living in a constantly changing world with increasing population and constraints on natural
resources are increasing day by day to alarming levels. This puts a severe pressure on technology,
increase in plant efficiency as far as existing plants are concerned, alternate energy sourcing and
recyclability to a great extend.
With a decline in conventional natural gas resources and with a recent increase in political desire to better
utilise clean burning natural gas, there is need for unconventional sources of Natural gas.
As more and more countries opened up economies, the trade barriers have started disappearing. The
result was not all that positive. Now each Ammonia (or any other syn gas plant in that way) plant has to
compete with any other international plant for survival. Rapid expansions of bigger ammonia production
groups also made the life of single train plants difficult. Political troubles could paralyse the feed stock
availability which we saw recently in certain parts of the world. Coal came back as a preferred source after
several years in certain geographical locations while presence of shale gas ( „fracturing“ became an
interesting word and now ranked above „drilling“ in certain parts of the world) changed the status of few
countries from HC importer to HC exporter. While these developments made revolutionary changes,
catalysts also underwent exciting modifications in terms of activity, selectivity and often life time yield. High
activity catalyst such as ReforMax® series, ShiftMax 120HCF & ShiftMax 200 series and AmoMax - 10 are
just few examples.
Profit pressures forced few companies to shutdown small capacity or single operated plants. Ammonia
plants that of 100 – 300 MTPD range stopped progressively in various locations in world. Also plants using
costlier feed Naphtha also became a rare species (despite few examples due to local government
pressure). Naphtha is still used in few refinery complexes where this is one of several feeds (depending on
availability) to produce Hydrogen. Here Hydrogen plant is considered as a utility plant. Simultaneous
usage of multiple feeds introduced several challenges on purification train (usually tightly designed) and
several unknown poisons were introduced in feed. Sourcing Gas from newer (and/or usually deeper) wells
was just one part of the story. Operating at low S/C caused metal dusting and rapid pressure drop growth
in Shift converters. Lack of catalyst and/or adsorbent stock caused sometimes an unscheduled shutdown
little longer further eroding the profitability. Despite the fact that individual catalysts have improved a lot in
terms of (both start of run and lined out) activity, selectivity and physical integrity, this was not completely
transferred into long catalyst life in Ammonia plants mainly due to reasons such as higher plant capacity
utilization, higher severity operation, presence of more poisons in the feed, reactor design limitation, leaner
operating staff coupled with decling experience, etc.
Last not the least, training of the operating staff is very important to maintain right knowledge to operate
the new generation plants with sensitive catalysts. Also in order to get maximum benefit from the latest
technology, we need to closely monitor the catalyst performance to predict the end of run condition and
plan shutdown window is a very important step in optimizing plant operation. We at Clariant enable our
clients to run their own performance predictions and plant optimizations by supplying (& training) easy to
use, tailored Ammonia & Methanol plant catalyst simulation models.
CATALYST STEPS
A conventional “Ammonia plant” based on steam methane reforming use several (up to nine in certain
case) catalytic steps depending upon the feed stock types starting from Natural Gas purification to
Ammonia Synthesis. Few plants also have a pre-reforming step in between purification and conventional
steam gas reforming step. In CO conversion section alone, we can see various combinations such as HTS
1/ 2, HT / LT, HT / MT / LT and MT / LT. In general each catalyst varies from other in terms of size, shape,
chemical composition, carrier (if any) and promoter etc.

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These various stages are described below.

Out of all the catalysts mentioned above Low Temperature Shift (LTS) Catalyst is considered as the most
sensitive catalyst in an Ammonia Plant closely followed by Pre Reformer catalyst. LTS is based on
Copper– Zinc chemistry (Our predecessor company was the first company to introduce LTS in to
commercial market and also the first company to patent the common plant design of HTS followed by LTS
with no CO2 removal in between) while Pre reformer is a high Nickel alumina catalyst operating at lower
temperature compared to other Nickel catalyst applications such as Primary or Secondary. The ability of
the pre reforming catalyst such as “ReforMax100“ to absorb any trace quantities of Sulfur remaining in the

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feedstock after purification without loss of activity is dependent on the retention of a high active metal
surface area.

In one of the case study we have conducted few years ago, we found that Low Temperature shift catalyst
contribute ~32% of the capital expenditure for the required catalyst volume of a new generation Ammonia
plant. However if you consider the total expenditure over a 10 year period with multiple catalyst
replacements, this figure further increases to 36 % as shown above.
Here LTS is the most sensitive catalyst in an Ammonia plant (somewhat similar to Pre reformer ) and also
considering the catalyst volume and reduction requirement can cause emergency shutdown which can
even be longer based on catalyst availability and reducing gas source.
Clariant offer self guarding Low temperature Shift catalyst such as ShiftMax 230 / 217 (low Methanol
version) , however also offer ShiftMax Cl CO Shift combined with Chloride Guard catalyst as top layering in
case of known Chloride poisoning history.
The performance of LTS catalyst has the highest impact on the profitability of an Ammonia plant as shown
below.

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Every 0.1% CO increase in CO slip can cause a production loss of 7 to 17 MTPD in 1000 MTPD of
Ammonia (worth 1,0 – 2,4 Mio USD per year).Needless to say that this effect will be higher for bigger
capacity plants such as 3300MTPD Ammonia.
PURIFICATION TRAIN CATALYSTS
Purification train catalysts is one of the main important step in Syn Gas plants as it conducts dual role in
feed stock preparation as well as protecting the downstream sensitive and very valuable catalysts.
Typically a combination of a reaction using a pre treatment catalyst, i.e. hydrogenation followed by the
ActiSorb adsorbent in one or two desulfurisation reactors. In certain plants only one DS step exist. Older
generation plants had single bed design such as shown below while new generation plants have high
active HDS catalyst followed by series lead lag desulfuriser arrangement (for maximisation of
desulfurisation ability).

First proof of non-functioning of purification train is the appearance of hot bands in Reformer. Given below
is the example the effect of higher sulfur entering Reformer and the subsequent effect on Methane slip and
tube wall temperature.

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 P. Kumar, N. Ringer

Also you see below the effect of higher tube skin temperature on the tube life.
Effect of tube wall temperature
Tube wall temperature Deg C Tube life ( hrs)
913 47,500
899 100,000
885 216,500

CASE STUDIES
Here we share few cases where optimised loading of purification catalyst helped the plants in getting
smooth operation for the poison sensitive catalysts.
Case 1
In one of the large capacity Ammonia Plants in MEA suddenly faced drastic reduction of LTS performance
as indicated by the slide below. Previous charge at this plant was ShiftMax230 catalyst from us but as we
could not supply LTS in time for the accidental shutdown they took the other type catalyst from nearby
plant and used. Detailed investigation at customer site and supplier’s end indicated that the LTS catalyst
was severely affected by Chloride and subsequent charge was loaded with complete modification of
Purification train (ActiSorbCl2 /ActiSorbS2) in Purification train and ShiftMaxCl / ShiftMax 230 in LTS
vessel. The performance at 110 % load was similar to the best operated LTS catalyst in the past which
was ShiftMax 230 at 100% load.

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LTS Performance comparison

LTS catalyst top LTS catalyst bottom

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Case 2
A large capacity Methanol plant faced severe pressure drop increase in HDS which caused occasional
shutdown (even caused organic Sulfur slippage to Reformer as Zinc Oxide was not capable to handle).
With suitable layering in HDS and DS vessels they could manage both the HDS pressure drop issue as
well as the occasional higher sulfur levels in the feed.
CONCLUSION
Purification trains performance is very important for all the Syn Gas plants and poor performance, incorrect
product selection / loading can cause significant operational upsets on downstream catalysts and can
affect the profitability of the plant. The subsequent damage can be four to five times the cost of maintaining
in the purification train intact.
ABBREVIATIONS
LDP – Low Differential Pressure
HTS – High Temperature Shift
MTS – Medium Temperature Shift Catalyst
LTS – Low Temperature Shift Catalyst
References
1. David Rice. Sued Chemie, The value of Catalyst performance in Ammonia Plants, AIChE 2002
2. David Borzik Misschem Nitrogen & David Rice Sued Cheme, Economics of Low Temperature Shift Catalysts in
Ammonia Plants, AIChE 2003
3. Nitrogen + Syngas 298 / March – April 2009, Adapting to a changing economy
4. Nitrogen + Methanol No 270 , Performance is the key
5. Prasant Kumar & Norbert Ringer, Clariant, Better understanding of chemical reactors, Nitrogen + Syngas 2014,
Paris

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