Design and Maintenance of Refractory

Linings in the Reformer Section of

Ammonia Plants

M. Ballon, M. Havlik, K. Schmalstieg and M. Wolske

KARRENA GmbH

1. Introduction The operational availability and the most

profitability of the production are associated

N ew technologies and the globalisation

of the markets increase
competitiveness of all branches and
industry companies. Increasing the
the
with maintenance strategies. “Maintenance”
has been developed to a real value-added factor
for commercial plants as illustrated in figure 1.

safety, reliability and efficiency are becoming The reported value of lost production is far
more importance for successful organizations higher than the direct maintenance costs
in the future. In this circumstance one of the (reproduced from [1]).
substantial items of commercial plant units is
the maintenance.

Figure 1: Results of survey of maintenance costs in 6 major companies

2006 165 AMMONIA TECHNICAL MANUAL

 The area of conflict between reactive measures “Minimise the loss of production with
in case of emergency and proactive moderate expenses for maintenance”
maintenance work is illustrated in Figure 2.

1.1 Maintenance of the refractory linings in

High
the reformer section of Ammonia plants.
About 75-80% Proactive
High temperatures and high pressures are
typical for the reformer section of Ammonia
Cost of plants. For this reason refractory linings are
Work
Optimized required in order to protect the steel vessels for
Work
the excessive process heat. The following
Low figure 3 is showing the main refractory lined
0% 20% 40% 60% 80% 100%
units of an Ammonia plant such as Primary and
Level of Work Executed in Advance of Asset Secondary Reformer, Process Gas Cooler,
Outlet Manifold System and Convection Bank.
Figure 2: Optimal Mix of Proactive and Each of these units has individual refractory
Reactive Work linings in order to meet the specific
requirements.
The targets for the maintenance of commercial
plants must follow the guide line:

Figure 3: Ammonia Syngas Plant [©UHDE]

AMMONIA TECHNICAL MANUAL 166 2006

 1.2 Control of the condition of the lining • design improvements
• material requirements and availability in
The most effective control of the refractory stock
linings has to be done during shut downs when
• specialists and labourers as well as
inspections enable the evaluation of the
equipment and tools etc.
conditions in front of the hot face skin. Such an
opportunity is always to recommend at all units
2. Primary Reformer
and at any shut down period although control
of water consumption at water jacketing, Synthesis gas necessary for production of
development of hot areas at steel shell sections, Ammonia will be generated by using the
fouling at heat exchanger tubes etc. can steam-reforming process in a Primary and
indicate irregular conditions of the linings even Secondary Reformer. The synthesis gas will be
during operation. lead through the catalyst tubes inside the
Primary Reformer box. The max. hot gas
Particularly the Hydrogen rich process gas can
temperatures are in the range of 1200 °C.
attack the refractory lining by Silica migration
out of the insulation layers and could cause
depositions at down stream units like the PG 2.1 Primary Reformer walls
Cooler. At higher temperatures and higher The walls are typically lined with insulating
pressures Hydrogen can remove Silica as per products. Most of the designs are based on
the following chemical reaction: using either insulating firebricks or ceramic
fibre materials.
SiO2 (solid) + H2 (gas) ÖSiO (gas) + H2O
(gas) 2.1.1 Insulating Fire Bricks

In areas where lower temperatures are existing The lining system above the tunnel walls is
condensation of SiO takes place. built up of insulating fire bricks and block
insulation for the back-up layers. The side wall
lining is supported by brackets at different
H2 + SiO Ö H2O + Si elevations. At these bracket areas expansion
joints are filled with ceramic fibre materials.
Fouling at heat exchanger tubes could be a During maintenance these expansion joints are
typical result of this chemical reaction. to be cleaned and refilled with ceramic fibres.
The condition of the hot face brick layer should
1.3 Preparation of Maintenance Activities be controlled with regard to cracks
The documents of previous inspections,
maintenance works and monitored operation
data are to be used for identification of the
required works and items to be prepared like:

2006 167 AMMONIA TECHNICAL MANUAL

 Figure 4: Insulating fire brick lining

Figure 5: Bracket Area Figure 6: Brick Lining

2.1.2 Ceramic Fibre Materials

Ceramic fibre walls at Primary Reformers
could be either designed with blankets or
modules. The ceramic fibre blanket lining is
consisting of different layers fixed by fibrefix
pins and clips/cuplocks. The number of layers
is dependent on the operating temperature and
heat flow through the wall.

Figure 7: Ceramic Fibre blanket lining

AMMONIA TECHNICAL MANUAL 168 2006

 blankets using a special method anyway.
Smaller joints will be closed again during
operation because of thermal expansion.

Picture 8: New CF blanket lining

During a shutdown the fixings arrangement are

to be checked. The blanket layers should be in
good shape. In case parts of the fibre blankets
are affected, the blankets can be replaced.
During these works the conditions of the
fixings are to be checked. Cuplocks and
washers might be replaced as well.

Figure 11: Method of filling joints in between

modules

2.2 Primary Reformer Floor

The typical lining starts from hot face with
special shaped high duty firebricks in the tube
passages and ends with insulating layers to
Picture 9: Ceramic fibre module lining of lower the temperatures of the bottom steel.
a transition section after 4 years operation

Picture 10: Roof Ceramic Fibre module lining

Ceramic fibre modules are fixed at the steel
shell by using different fixing systems.
During shutdown such a lining is to be checked Figure 12: Overview Floor
with regard to the size of joints between each
module. Bigger joints of let say more than 10
mm width must be filled with ceramic fibre

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 High duty
Insulation bricks
walls, cover slabs are made of similar grade of
material. During maintenance all expansion
joints are to be cleaned and filled with ceramic
fibre blanket in order to enable proper
Block Insulation
expansion during the next run and to seal the
or castable tunnel walls.

Block
insulation or High duty firebricks Expansion Joint
castable
Insulation bricks

Ceramic fibre
material

Figure 13: Details Tube penetration

Picture 14: Expansion Joint and

During shutdown cleaning of the floor and Tunnel cover slabs after 5 year
replacement of the expansion joint filling is of operation
required

2.3 Tunnels Furthermore the cover slabs must be checked

for cracks and spalling, and needs to be
Particular attention must be given to the design
documented and observed for the next
of the flue gas tunnels with regard to the
shutdown. In case of serious damages the
pressure difference between outside and inside
blocks need to be renewed.
of the tunnels. The typical design of the tunnels
is considering high duty fire clay bricks for the

Figure 15: Tunnel Walls

AMMONIA TECHNICAL MANUAL 170 2006

 maintenance of the roof lining is similar to the
ceramic fibre walls.
In case of using ceramic fibre blankets for the
roof lining special attention has to be paid to
the fixing arrangement by cuplocks. Because of
high temperatures and sometimes due to
vibration of the burners the cuplocks tend to
getting loose. Therefore at least the visual
inspection is important and re-fixing of the
cuplocks as required.

Picture 16: Damaged cover slabs (after 10 3 Outlet Header System / Transfer Line
years of operation period)
The process gas of the tubes of the Primary
Reformer is collected in the outlet header
2.4 Roof system. The refractory lining system of the
header system is consisting of insulating
Most of the current roof designs are based on castable for the back-up lining covered by a
ceramic fibre linings - again - either designed metallic liner or a dense castable as illustrated
as blanket or module lining. The required in figure 17.

Figure 17: Two different lined Header systems

2006 171 AMMONIA TECHNICAL MANUAL

 Normally no maintenance activities are endothermic process to approx. 1.000 °C. The
required. Renewal of seals on header/transfer operating pressure of modern units is around 40
blind flanges regularly to be opened for bars. Due to the catalyst in between gas inlet
inspection is required. During changing of the and outlet of the Secondary Reformer a
reformer tubes all “donut-bricks” (special pressure drop which is limited to a certain level
shaped bricks) should be checked and replaced has to be compensated by the catalyst vault
if required. which has also to carry the weight of the
catalyst.

4 Secondary Reformer It is extremely important that the refractory

design does not enable process gas bypassing
The process gas leaves the primary reformer through the lining. For this reason the hot face
and will be fed into the Secondary Reformer. layer material has to have low gas permeability
The feeding temperature of the process gas is in and the expansion joints are to be closed during
the range of 800 - 850°C. operation of the unit at higher temperatures.
The gas temperature will be increased at the
Secondary Reformer combustion section to
approx. 1.300°C whilst passing the catalyst the
gas temperature will be reduced by the

High Alumina
Refractory Bricks

Bubble Alumina High Alumina

shapes Castable
Bubble Alumina
Insulating Layer

Synthesis gas
flo

Figure 18: Secondary Reformer of different designs

AMMONIA TECHNICAL MANUAL 172 2006

 It is important to know that the vertical and The joints are to be cleaned, grains or dust
horizontal expansion joints are determined in should be removed. The condition of the bricks
accordance with the design temperature, i. e. around the joints has to be checked with regard
during cold shutdown the joints must be to the edges, quantity of cracks and spalling.
opened and during operation closed again.
Operating temperatures above design would The radial expansion joints are required at all
cause additional forces induced by the non free sections of the Secondary Reformer lining in
expansion. order to enable free thermal expansion of the
lining.
The vertical and horizontal expansion joints
must be checked and maintained during each The total joint thickness, i.e. the cumulated
shut down period. figure of all joints around the circumference of
the brick ring is to be checked in accordance
The joints are to be cleaned, grains or dust with the design documents. Cleaning of the
should be removed. The condition of the bricks joints is very important to avoid any damages
around the joints has to be checked with regard as a result of non free thermal expansion of the
to the edges, quantity of cracks and spalling. lining.
The vertical and horizontal expansion joints
should be checked and maintained during each
shut down period.

Expansion
Joint, check
and keep clean

Figure 19: Typical horizontal joint Figure 20: Typical radial expansion joints

2006 173 AMMONIA TECHNICAL MANUAL

 very important. Special attention has to be paid
to the transition area of the tube sheet lining
and cylindrical brick lining as well as the lining
of the conical section. Maintenance activities
are limited to checking of the expansion joints,
as well as cleaning and re-filling - if required-
during each shutdown period.

High Alumina
Refractory
Insulation
Material
Picture 21: Detail of the expansion joint after
approx 10 years operation time

Heat
Exchanger

From
Secondary
Reformer

Figure 23: Detail of PG-Cooler Lining (Inlet

Chamber
Picture 22: Typical cracks of the lining after
approx 10 years operation time High Duty
Refractory Material
Insulation
Rounded brick edges and glazy hot surfaces are Material

caused either by very high operation

temperatures (glasification) or in general with
the advanced operation time period.
Risk analysis for any further operation requires
experienced specialists.

5 PG-Cooler
The synthesis gas of the Secondary Reformer
will be introduced to the inlet chamber of the
PG-Cooler (Process Gas Cooler). The gas
temperature is in the range of 1000 °C and the Figure 24: Detail of PG-Cooler Lining (Outlet
gas pressure is around 40 bar. The gas will be Chamber)
cooled down by passing through the heat
exchanger tubes to the outlet chamber. The PG-
Coolers are typically lined with a dense 6 Moderate Operation
material for the hot face layer and an insulating Immoderate operation can cause extreme
back-up layer. damages to the refractory linings of the
Due to the process conditions and the turbulent different plant units. Some items are to be
gas flow, the integrity of the refractory lining is considered relevant in this circumstance like:

AMMONIA TECHNICAL MANUAL 174 2006

 - operating temperature
- dry-out and initial heating-up 400

ΔT =10 K ΔT =10 K
- heating-up and cooling down cycles and

HOT GAS TEMPERATURES [°C]

rates 300

- pressurisation and depressurisation rates

/h

max.
°C
10
curve not
200

x.

30 °C
true to scale

ma
hold for 48 h

/h
Indications about the condition of the 130
100

refractory system can be kept by analysing X

20
operating data like the temperature of pressure DURATION [h]

shells, higher water consumption in case of x = without regulation

water jacket, fouling at the heat exchanger

tubes caused by Silica removal from the Figure 25: Typical dry-out curve
refractory insulation layers etc.

HOT GAS TEMPERATURES [°C]

service temperature

6.1 Operating temperature 800

X
m
ax
.3
700 0
°C
For the integrity of the lining it is always curve not
/h

/h
600
true to scale
important to consider the design conditions of

50 °C
500

max.
the plant unit. The selection of the most 400

suitable refractory system and the design is 300

/h
precisely based on these conditions. 200
ax
.2
0
°C

130 m
100

One of the most important properties of 20 X

DURATION [h]
x = without regulation
refractory products is the classification
temperature of the materials. The hot face
Figure 26: Typical heating-up curve
temperature plus an addition of 100-150°C will
determine the classification temperature of the Dry-out of the refractory lining is the advanced
refractory materials. process of initial heating-up for most of the
plants, particularly important in case the initial
6.2 Dry-out and initial heating-up heating-up requires increasing of the inside
pressure of the units.
Dry-out and initial heating-up of the refractory
lining is an extremely important process which Always bear in mind that the refractory lining
requires consideration of particular items. in a common size of new installed Secondary
Water required for working with unshaped Reformer contains approx. 20-25000 litre
refractory materials will be kept in the set water. In case the unit will start operation
bounding matrix as physically adsorbed water without prior dry-out the water will be not
and chemically bounded as part of the removed because of the high pressure inside.
hydraulic bounding system. The physically This can be verified by considering the phase
bounded water has to be removed during dry- diagram for water. This diagram is clearly
out at temperatures in the range of 100-200°C showing that the water will be held in the
whilst the chemically bounded water will be unchanged modification when the unit operates
removed at higher temperature above 450°C at high pressures. In the unlikely event that the
during initial heating-up. inside pressure during operation will be
uncontrolled and suddenly decreased the water
will immediately be vaporised by an extreme
volume increase, an effect similar to an
explosion.

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 6.4 Pressurisation and depressurisation
Pressurisation and depressurisation always
need to be done very carefully because of the
nature of refractory products with the inelastic
material structures and the less gas
permeability of the hot face layer material
typically installed in Secondary Reformers and
PGC inlet chambers.

Refractory linings with more than one layer

will exceed pressure equalisation as a function
Figure 27: Phase diagram for water of time in case of non open gaps and joints.
The time required for pressure equalisation is
6.3 Heating-up and cooling down mostly a function of the gas permeability of the
dense refractory layer, only. In case of a too
During heating-up it is important to avoid too fast depressurisation the gas trapped in the
high thermal gradients at the layers. back-up layers cannot escape fast enough due
to the more or less dense hot face layer. This
The different thermal expansion of the hot and can cause considerable damages to the lining
back sides of each layer could cause stresses in system. KARRENA has developed an own
the refractory matrix which could result in computerised program for investigations on
spalling and cracking. Tensile stresses are pressurisation and depressurisation of
effectively damaging the back side of the layer refractory linings of synthesis gas units. The
during too fast heating-up. current state of the results with regard to proper
pressurisation and depressurisation rates is
Stresses inside the layer shown in figure 29.
during heating-up

T hotface > T backside

ΔP=2,5bar ΔP=2,5bar
∆L

↑ ΔP=2,5bar ΔP=2,5bar
0,5
/min

bar
bar
tensile stresses

/min
0,5

T hotface T backside
in
in

in
in
5m
5m

5m
5m

↓
∆L
Figure 29: Typical pressurisation and de-
pressurisation rates
Figure 28: Stresses inside the layer during
heating-up The quantity of gas passing through the
refractory system depends on the gas
During cooling down the effects inside the permeability of the dense layer with the lowest
layer are basically the same but vice versa. Too amount of open pores. This is the layer relevant
fast cooling down will induce tensile stresses at for specifying pressurising and depressurising
the hot face skin of the layers due to the rates.
different temperatures inside the refractory
matrix.

AMMONIA TECHNICAL MANUAL 176 2006

 7. Documentation
Proper visual inspection, measurement of joints
and photo documentation during each
shutdown will enable a proper evaluation of the
lining condition and will clearly indicate
required activities in the future. Such well
prepared maintenance documents are forming
the integral basis for works to be planned
during the next shutdowns.

8. Appendix
[1] Leonie Gouws, Adrian Stephan and James
Trevelyan: The nature of engineering maintenance
work: a blank space on the map, School of
mechanical engineering, The University of Western
Australia 2006

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