Pushing the Limits – Breakthrough

in Pre-Reformer Design
This paper summarizes properties of a new generation of pre-reforming catalysts by publishing
detailed research and pilot test data as well as operating experience in a commercial application
in a pre-reforming unit of a 1360 mtpa NH3 plant. This data lead to significant re-evaluation of
pre-reforming units design criteria. In addition the paper indicates an outlook on feasibility of
pre-reforming units for new plants as well as attractive revamp options for existing plants.

Ingo Hanke and Norbert Ringer

SÜD-CHEMIE AG

Introduction Pre-reforming catalysts are manufactured utilization

of precipitation. The most important active component

P re-reforming is the steam reforming of meth-

ane or higher hydrocarbon components and
methanation of carbon-monoxide and car-
bon-dioxide in presence of hydrogen and simultane-
ously water gas shift.
of pre-reforming catalysts is Ni. Typically pre-
reforming catalysts are installed in an oxidized state and
reduced prior operation in-situ. In case reduction in-situ
is not suitable pre-reduced catalyst can be installed.

CxHy + xH2O = xCO + (x+1/2y)H2 Market Information

CO + 3H2 = CH4 + H2O
CO +H2O = CO2 + H2
The pre-reforming effluent gas contains CH4, CO,
CO2, and steam at thermodynamically equilibrium and
act as an ideal feedstock for the steam reformer furnace.
Historically the pre-reforming process was devel-
oped in the early 60s to produce town gas or substitute
natural gas utilizing naphtha as feedstock. Later pre-
reforming units are utilized for gas-making units or in-
tegrated process units of hydrogen, methanol or ammo-
nia plants upstream of the steam reforming unit.
Pre-reforming is carried out in the vapor phase over a
catalyst, which is installed as an adiabadic fixed bed sys-
tem. Typical Operating temperatures are in the range of
400 to 500 °C and operating pressures are typically in the
range of 20 to 30 bar. Depending on feedstock composi-
tion pre-reforming can be endothermic or exothermic.
Historically pre-reforming units have been installed
since the early 1960s mainly for gas making applica-
tions such as town gas plants utilizing heavy hydrocar-
bon feedstocks e.g. butane or naphtha.
Todays total installed volume of pre-reforming
catalysts in syngas plants of approx. 750 mt world-wide
can be broken down to
• 30 % installed in hydrogen plants
• 38 % installed in methanol plants
• 32 % installed in ammonia plants
The percentage of pre-reforming units integrated in
installed syngas plants amount to
• 4.7 % of the hydrogen production capacity
• 7.0 % of the methanol production capacity

AMMONIA TECHNICAL MANUAL 152 2003

 • 3.6 % of the ammonia production capacity
The relative low numbers is still resulting from his-
tory, where pre-reforming units have mainly been inte-
grated in plants utilizing heavy hydrocarbon feedstocks
for the production of syngas mixtures to produce hydro-
gen, methanol or ammonia. Therefore geographically
pre-reforming units are mainly located in South Europe
and India. Due to poor economics and increased product
purities as well as requirement of increased turn around
periods heavy feedstocks have dominantly been rejected
as syngas plants feedstocks.
But, over the last years increasing economical pres-
sure on syngas producers, technology and engineering
companies increased and therefore design approaches
changed. Pre-reformer have increasingly applied to syn-
gas plants to benefit from increased plant energy effi-
ciency, capital savings from smaller and more reliable
steam reformer operation, feed flexibility and plant up-
grades. This is how pre-reforming founds it’s place in
new plant concepts and retrofits.
Today about 25% of all new syngas plant designs
propose a pre-reforming unit. In addition a high number
of plant retrofits propose pre-reformer units in existing
plants to upgrade plants capacity and energy consump-
tions figures by installing a pre-reformer unit in the ex-
isting plant. Both applications combined result in an
annual increase of installed pre-reforming units of more
than 15,0%.
Basic Process Features
Looking at pre-reforming as a design item the main
process equipment consists of a simple single phase
fixed bed reactor. Utility lines for reduction, regenera-
tion as well as unit start-up and shut down procedures
as well as a reactor bypass line including quick isola-
tion valves have to be installed based on licensor or
catalyst manufacturer requirement. The reactor volume
is defined by catalyst design requirements depending on
process conditions and overall unit design and opera-
tion strategy. Typical design requirements are steam to
carbon ratio, space velocity and catalyst activity factors
depending on thermodynamical process conditions.
Next to high space velocities allowing small reactors
and therefore cost effective unit designs long lifetimes of
the installed catalysts allow long operating periods with-
out shut downs. In addition long catalyst lifetimes di-
rectly reduce costs by catalyst replacement requirements.
Since steam reforming reactions are a combination
of reforming, methanation and water gas shift reaction
2003
the overall reaction can be exothermic as well as endo-
thermic. In case of heavy feedstock composition the
pre-reforming reactor perform temperature increase and
light hydrocarbon feed-stocks perform temperature de-
crease during normal operation.
Therefore pre-reformer can be incorporated in flow-
sheets of syngas plants with and without heat integra-
tion. The endothermic pre-reforming of light feedstock
allows the reactor effluent to be reheated in the primary
reformer duct, which offers energy efficiency benefits.
In most applications the process offers the most advan-
tageous heat integration if the reactor is operated at
high operating temperature levels.
Main features of the pre-reforming unit as an oper-
ating plant are in addition to the above features low
sensitivity of process parameters for capacity changes
as well as easy start-up and shut down procedures.
Laboratory Results
Süd-Chemie’s approach to develop a state of the art
catalyst as benchmark for pre-reforming catalysts
started in the mid 90s. Verifying the importance of pre-
reforming units for flexible feedstock grass root syngas
plants as well as for plant up-grades Süd-Chemie fo-
cused on a systematic approach. State of the art analysis
tools and methods as well as the design of a computer
automated pilot test unit establish reproducible labora-
tory test results.
In general the laboratory test work can be sepa-
rated into activity, stability tests and tests for special
properties. After defining of a standardized reference
test method and screening of various laboratory cata-
lyst preparations the most promising laboratory prod-
ucts have been transferred to an up-scaled pilot pro-
duction plant and tested in the pilot unit.
In the following test results selected out of a high
number of laboratory tests from the test program are pre-
sented to highlight state-of-the-art pre-reforming catalyst
properties. Related to the most relevent properties of pre-
reforming catalysts results related to activity, poison re-
sistance and stability tests are selected. Test conditions
for all tests of the test program are typically high space
velocities and reference temperature and pressure utiliz-
ing a standardized naphtha feedstock composition.
The following figure 1 indicate activity test results
of representative pre-reforming catalysts based on
desulfurized virgin naphtha feedstock. The activity is
defined as conversion of C5/C6 hydrocarbons, which is
related to time on stream under standardized test condi-
tions. The test results indicate different levels of pre-
reforming catalyst activity.
153 AMMONIA TECHNICAL MANUAL
 Figure 1. Laboratory Results: Pre-Reforming Catalyst Activities.

Figure 2. Laboratory Results: Pre-Reforming Catalysts Poison Resistance.

The test results indicated in Figure 2 show poison
resistance test results of representative pre-reforming
catalysts based on sulfurized virgin naphtha feedstock.
Again, the activity is defined as conversion of C5/C6
hydrocarbons and presented as a function of on stream
time. The test results indicate different levels of poison
resistance of pre-reforming catalysts.
Besides activity and poison resistance the stability
of the catalyst is responsible for an optimized lifetime
of the pre-reforming catalyst. Therefore stability tests
according to activity test as described above focusing
on an increased test period have been carried out to ver-
ify lifetime expectations for commercial plant applica-
tions. Figure 3 indicates catalyst activities up to a time
on stream of approx 65 hours for two qualified catalyst
products. Based on reliable tools for up-scaling test re-
sults to commercial plant performance data catalyst life-
time projections can be carried out for the individual
pre-reforming reactor scheme.
Moreover the test program included a high number
of analytical tests and analysis on mechanical and
chemical properties of selected catalysts. As an exam-
ple test on steaming resistance should be mentioned.
Steaming resistance is important for several situations

AMMONIA TECHNICAL MANUAL 154 2003

 Figure 3. Laboratory Results: Pre-Reforming Catalysts Stability.
during the catalyst life cycle and most important for
start-up and shut down operational procedures of the
unit. Moreover, next to advanced mechanical properties
such as high crush strenth steaming resistance is impor-
tant to be able to keep the catalyst active during unex-
pected operational situations. The most likely unex-
pected situations are
• Trip of the up-stream or down-stream process
units and therefore loss of feedstock/steam
• Coking of the catalyst by operation at low S/C
ratio
• Carry over of liquid water to the catalyst bed
by upstream mechanical equipment failures or
mal-operation
• Regeneration of the catalyst by steaming pro-
cedure of the catalyst in-situ after poisoning
Main result of the steaming resistance tests on the
commercial pre-reforming catalysts are the verification
of the steaming resistance of the catalyst up to a steam-
ing period of approx. 24 hours. This result is essential
to propose a lean unit design! Quick isolation valves in
the bypass lines of pre-reformer units are not required
to protect the catalyst. Moreover, the requirement for a
bypass line itself has to be discussed based on unit de-
sign philosophy and reliability analysis during design
stage of a new pre-reforming unit.
Performance Data
Transferring the basic understanding on what is re-
quired for designing and manufacturing on f pre-
2003
reforming catalyst based on the results of the research
and development program described above SÜD-
CHEMIE was able to successfully introduce the new
C-11PR catalyst series on the market in the late 90s.
To demonstrate the performance of the new product in
the following the performance data of an European
1360 mtpd NH3 plant designed by Foster Wheeler are
highlighted.
In figure 4, the temperature profiles of the pre-
reforming catalyst bed are illustrated over a operating
period between April ‘98 and November ‘00. This pe-
riod of time includes a shut –down and replacement of
the catalyst, so two types of catalyst performances can
be compared directly.
The temperature profile shown as typical for exo-
thermic pre-reforming reaction of natural gas, which re-
sults in an temperature increase over the catalyst bed of
approx. 40°C. The differential temperature between re-
actor inlet and reactor outlet is a direct consequence on
the chemical reactions of the pre-reforming unit de-
scribed earlier in this paper and therefore can be under-
stood as a direct measurement of activity of the pre-
reforming catalyst.
Looking at the differential temperature over a period
of time of approx. 18 months it can be noticed that the
performance after the catalyst replacement is somehow
similar to the period before replacement. In detail the
temperature profile seems to be more equally established
and on a slightly higher level, but it has to be kept in
mind that the replaced catalyst worked at end-of-run and
the fresh catalyst at start-of-run operating condition.
In the following figure 5, the operating data of the
above described reference unit illustrated by indicating
155 AMMONIA TECHNICAL MANUAL
 Figure 4. Reference NH3 Plant Data.

Figure 5. Reference NH3 Plant Data.

the reactor outlet dry gas space velocity over a operat-
ing period between March ‘00 and May ‘02.
Due to a mechanical failure at the plant outside of
the pre-reforming unit the originally loaded catalyst
was again replaced in December ‘00. Moreover due to
availability of the catalyst quantity on the catalyst
emergency stock the installed catalyst volumes for op-
eration after this second replacement periods have been
significantly smaller, which in fact lead to short loaded
catalyst volumes. As a consequence of this the catalyst
was operated for a period of approx. 20months at high
loads, respectively space velocity.
Based on the above laboratory results and commer-
cial plant performance data the space velocity require-
ments for new pre-reforming units utilizing natural gas
feedstocks result in significantly reduced catalyst vol-
ume requirements.
Pre-Reforming for New Plants
Pre-Reforming concepts for new plants are based
on the proposal to utilize different feedstock qualities to
gain operating flexibility. Besides operation on natural
gas alternative design cases proposing naphtha, propane

AMMONIA TECHNICAL MANUAL 156 2003

and butane feedstocks. The benefits from integration of • The existing heat exchange is modified.
a pre-reforming units are of qualitatively character and • The originally S/C ratio is adjusted.
can be summarized to • Additional fired heater capacity is installed

• Decrease of feedstock contamination by poi- The estimated total investment for equipment
sons of the feedstock to the primary reformer amounts to 2,4% of the total investment for the ammo-
• Increased primary reformer inlet temperature nia plant prior up-grade.
flexibility The simplified cost estimation presents advantages
• Decrease of minimum steam/carbon ratio of the for pre-reforming versus increased reforming capacity
primary reformer related to invest cost evaluations.
• No requirement of promoted primary reform-
ing catalyst
• Increase of lifetime of primary reformer cata- Conclusion
lyst and tubes The scientific approach of SÜDCHEMIE on devel-
• Decrease of primary reformer heat duty for op- oping a new pre-reforming catalyst lead to promising
eration by heavy hydrocarbon feedstocks laboratory data and subsequently after successful up-
• Reduced carbon formation in the top section of scale of the first generation to a commercially bench-
the primary reformer tubes mark pre-reforming catalyst product. Moreover the
commercial reference plant data lead to significant re-
duction of required catalyst volumes as well as a simpli-
Options for Plant Up-Grades
fication of operating procedures and therefore result in
In general pre-reforming is considered to be attrac- increased feasibility considerations for both grass root
tive to up-grade existing syngas plant capacity. In the plants and plant up-grades.
following the revamp of a 1360 mtpd ammonia plant
resulting in 20% capacity increase is evaluated for utili-
zation of natural gas as feedstock. The revamp of the
reforming section is executed by adding additional re-
forming capacity to the plant and alternatively by in-
stallation of a pre-reformer. The consideration is focus-
sed on the reforming section as the key focus of the up-
grade activity. All other plant units as well as the spe-
cific steam balance and energy consumption are consid-
ered to be unchanged. Shut down times of the plant to
be revamped have not been considered.

Investment Costs Base Case

• Additional 20% reforming capacity is installed.

• Additional 20% combustion air capacity is in-
stalled.

The estimated total investment for equipment

amounts to 2,9% of the total investment for the ammo-
nia plant prior up-grade.

Investment Costs Alternate Case

• New pre-reforming unit is installed.

• Additional 10% combustion air capacity is in-
stalled.

2003 157 AMMONIA TECHNICAL MANUAL