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PUSFI
PUSRI- IIB PROJECT
2OOO
MTPDAMMONIA& 2750 MTPDUREA t aTOYO

PRODUCT
BROCHURE
PRIMARY
REFORMER (101.8)
CATALYST

' 06 Cci
CLARIANT- 2014

PT.CLARIANTKUJANGCATALYSTS

OWNER PT. PUPUKSRIWIDJAJAPALEMBANG

CONTRACTOR CONSORTIUM .
OF PT. REKAYASAINDUSTRI
TOYOENGINEERING
CORPORATION

PROJECTTITLE PUSRI-IIB PROJECT

LOCATION PALEMBANG, INDONESIA

SOUTHSUMATERA

JOB NO. r2.1812/8A1066

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NAME. PrimaryR€formerCatalyst

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1 3 Ocl.2014 lssuedfor lntormation IKH RH

0 21 Aotil 2014 lssuedfor Information IKH
REV,NO. DATE DESCRIPTION PREPD CHKD APPVD
 JOBNO.: 12-1812l8A1066
PRODUCTBROCHUREPRIMARYREFORMER
CATALYST
(r01-B)

REVISION
HISTORICAL
SHEET

Rev.No. Date Description

0 2l Aptil2014 lssuedfor Information

1 3 Oct.2014 lssuedfor Information
 Product Bulletin

Issue, April 2014

PUBLISHER
PT. CLARIANT KUJANG CATALYSTS
CONTACT
For further information or
support, please contact
sales@clariant-kujang.com

Catalyst for
FIRED HYDROCARBON REFORMING
 Catalyst for
Fired Hydrocarbon Reforming
ReforMax@ 210 LDP

CONTENT

General ............................................................................................................................. 1

Product features................................................................................................................ 2

Applications ...................................................................................................................... 5

Poisons ............................................................................................................................. 5

Technical services ............................................................................................................. 6

Guarantees ....................................................................................................................... 7

Shipping information ........................................................................................................ 7

What is precious to you?

 GENERAL
The hydrocarbon steam reforming process is the
principal industrial process used to manufacture
synthesis gas for the production of hydrogen,
ammonia and methanol. The heart of this process
is the tubular steam reformer where the
hydrocarbon feed plus steam is catalytically
reacted to produce the synthesis gas. In ammonia
plant, tubular steam reformer that usually called
primary reforming is followed by an autothermic
reforming process i.e. secondary reformer to
finalized methane reforming and air injection as
nitrogen source for ammonia production.
Meanwhile in modern methanol plant, it is
followed by auto-thermal reformer where high
purity oxygen fed to finalized methane reforming
as specified.

The Clariant Group (fomerly: Süd-Chemie) has

manufactured the fired hydrocarbon reforming
catalysts over 50 years, providing a complete
range of the catalyst such that selection can be
made of the most effective catalyst for any
condition of process feed and process design. The
products, which in all forms contains nickel as
active metal has been developed continuously to
respond users desire where they favor to choice
the catalysts that having characteristic of high
activity, low pressure drop, high physical strength
and more resistance to poison. Clariant Group
also has developed nickel based fired hydrocarbon
reforming catalysts contain potassium which is
fully incorporated into the catalyst carrier to
minimize the formation of carbon. This allows
using widely range of feedstock for hydrocarbon
steam reforming, such as light to heavy
hydrocarbon, LPG and naphtha.

ReforMax@ 210 LDP is one of potassium promoted

fired hydrocarbon reforming catalyst produced by
Clariant that is used for reforming light to heavy
hydrocarbon and LPG feedstock in hydrocarbon-
steam tubular reformer. The original name is G-
91 LDP. Replacing product name was done in line
with Clariant’s simplifying product nomenclature
in order for the customer to more easily recognize
the products and their usage.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 1


PRODUCT FEATURES
Similar to ReforMax@ 330 LDP type, ReforMax@ 210
LDP is the product type that has excellent in low
pressure drop and high geometric surface area
comparing to another types. The different between
these catalysts is the ReforMax@ 210 LDP type is
promoted with potassium for coke resistance
improvement. It allows using the catalyst for
heavier hydrocarbon and LPG feedstock. The
catalyst has two standard sizes i.e. 19x16 mm and
19x12 mm. It has gray appearance, no odor,
insoluble in water and melting point is more than
1900oC. It is negligible fire and explosion hazards
when exposed to heat or flame by reaction with
incompatible substances.
The catalyst performance in a tubular steam-
hydrocarbon reformer cannot be discussed in
terms, which would be generally applicable to all
reformers. Most users equate performance with life
as manifested by catalyst strength. This is due to
the fact, that the vast majority of reformers are
designed so conservatively that virtually any
reforming catalyst will demonstrate satisfactory
performance as long as the catalyst remains
physically intact. Some of the more modern high
severity reformers are much less conservative in
design and as a result localized catalyst activity
becomes the limiting feature of the catalyst, as high
activity must be maintained to maintain tube skin
temperatures within allowable limits. Even in
furnaces where localized activity is a major criteria,
strength may be become the limiting factor as some
very active catalyst demonstrate very poor strength
characteristics with the result that when the
catalyst loses physical integrity, premature catalyst
change-outs due to physical or strength
considerations.
ReforMax@ 210 LDP visualization
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
Typical properties of ReforMax® 210 LDP
Nominal Content, wt% ReforMax® 210 LDP
Nickel Oxide 18
Potassium Oxide 1.5
Carrier, Ca-Aluminate Balance
Shape 10 Holed Ring
Size, mm 19x12; 19x16
CATALYST SHAPE
With respect to surface area, it is evident that the
simplest and most effective way to maximize
catalyst activity is by using catalyst particles with
highest external geometric surface area. At first
this was accomplished by using smaller size rings
on the expense, however, of increasing pressure
drop. A breakthrough came in 1978 when
Clariant Group developed the first high geometric
surface shape, a seven-spoked wheel, which
provides approx. 60 percent higher activity
compared to the standard ring. This seven-spoked
wheel shape is called EW shape, standing for
enhanced wheel.
The Clariant Group always was the leading
company in developing more sophisticated shapes
comprising maximum geometric surface area
while at the same time featuring low pressure
drop. The latest product shape development is the
LDP shape. LDP stands for low differential
pressure. As it is the case for EW shape, the LDP
shape comprises high geometric surface area,
thus high activity for the steam reforming
reaction. The most striking feature, however, of
the LDP shape is the combination of high activity
with extremely low pressure drop.
ACTIVITY
Catalyst activity is determined by surface area
and active metal content. High activity means
faster reaction rate will be occurred. Relating to
tubular reformer, the activity also affects tube
wall temperature; depend on sections of the tube.
 Surface area:
In the tubular reformer, gas diffusion into the
catalyst pores is the essential step for overall
reaction rate. Almost of the reaction takes
place on the outer surface of the catalyst
2
 particle. Thus, higher activity will be achieved
for the catalyst with higher surface area.
LDP series 19x12
LDP series 19x16
EW series 16x6
Rib-ring 16x16x6
Ring 16x10x8
Ring 16x16x6
- 50 100
Relative GSA, %
 Nickel content:
Nickel (Ni) is catalytically active component of
any commercially available steam reforming
catalyst. Therefore, one can assume that
increasing content of nickel will also increase
the catalyst activity. This is true only to a
certain extent. The optimum nickel content is
around 14 to 18 %-wt as Ni.
40
35
Reaction
30 rate
x 1000
25
20
15
10
5 The initial pressure drop is determined by the
0
4 8 121620
Nickel content, %-wt
 Tube wall temperature:
Tube costs are a significant item in the overall
economics of a reforming plant and it is good
practice to operate the reformer with the tube
wall temperatures as low as possible consistent,
of course, with satisfactory reformed gas quality.
Even a slight increase in the tube wall
temperatures will have a drastic impact on the
tube life. When the maximum tube wall
temperature is increased by only 10oC it may
result in an up to 30 percent shortened lifetime
of the reformers tube.
The effect of the catalyst activity on the tube
wall temperature can vary significant with
furnace design and operation and requires for
an understanding a closer look to the
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
relationship between activity and heat transfer.
The heat transfer from outer surface of tube to
the center of the catalyst is represented by the
equation as follows: Q/A = U (TOW – TG), where;
Q/A: heat flux
U: overall heat transfer coefficient
TOW: outer surface of tube temperature
TG: gas inside tube temperature
About 70 percent of the heat flux is used in the
reforming reaction and remaining is for the
sensible heat. In sections of the tube where the
reaction is far away from reforming equilibrium, a
more active catalyst can achieve more
150 200 endothermic reforming and will hence consume a
larger part of the incoming heat which will result
in a lower gas temperature in that region. This will
allow the same amount of heat input starting with
a cooler outer tube wall temperature.
However, in regions of the tube where the gas
already close to the reforming equilibrium, a more
active catalyst cannot achieve additional
reforming and there will be little effect on the
temperature of the gas and of the outer tube wall
in that section
PRESSURE DROP
Everything related to pressure drop is most
critical in the operation of the tubular reformer.
One has to consider both, the initial pressure
drop and the evolution of the pressure drop with
time on stream.
 Initial pressure drop:
catalyst shape and to a certain extent by the
loading method. Laboratory test shows
24 pressure drop of ReforMax@ 210 LDP is much
lower than other types. This means loading
ReforMax@ 210 LDP type allows running higher
throughput rate at the same pressure drop to
other types.
 Time on stream pressure drop:
The catalyst loaded in the reformer tubes is
subject to extreme physical stress due to the
expansion and compression of the tubes
during plant start-up, shutdown and upset
conditions. High crush strength is necessary to
prevent catalyst breakage due to those
problems. The carrier of catalyst composition
has important effect to build catalyst that
having high crush strength. The Clariant
Research Group has found hibonite type
carrier that also known as CaAl12O19 which is
the only irreversible formed phase in the
CaO/Al2O3 phase diagram. This is the reason
3
 for the extreme stability over physical and  Carbon formation reactions:
thermal stresses of reforming catalysts that The carbon can be formed under the reactions
using this carrier type. The ReforMax@ 210 LDP as follows:
catalyst uses hibonite carrier type which is
incorporated with potassium oxide (K2O) for
coke resistance. Similar to ReforMax@ 330 LDP 1) Thermal or catalytic cracking:
type, the catalyst has much higher crush CH4==== C + 2H2
strength than other types 2) Boudouard reaction or CO disproportion:
2CO==== C + CO2
3) CO reduction:
▪ What’s more dominant ? CO + H2==== C + H2O
As long as extreme physical stress can be 4) Reverse water-shift reaction:
avoided even if during plant start-up, CO2 + 2H2==== C + 2H2O
shutdown or upset conditions; then breakage
of catalyst would be hindered and pressure
drop across catalyst bed is primarily Carbon formation from CO is 3 to 10 times
determined by catalyst shape. faster than methane. At high temperature, CO
disproportion is faster than CO lowering water-
shift reaction. Reaction (3) and (4) show the
potential of steam to remove carbon.
LDP series 19x12

LDP series 19x16  Carrier or support:

Resulting carbon will deposit on catalyst
EW series 16x6 surface causes deactivated catalyst, catalyst
break-up and catalyst overheating. The
Rib-ring 16x16x6 suppression of carbon formation reactions is
accomplished by decreasing the acidity of the
Ring 16x10x8 catalyst by incorporating alkaline earth metals
into the carrier and by further promoting with
Ring 16x16x6 an alkali metal. The most common commercial
combinations used are potassium promoted
- 50 100 150 calcium aluminate and potassium promoted
magnesium aluminate. The combination
Relative Pressure drop, % retards the formation of carbon and also
accelerates the carbon gasification reaction
once it has been formed.
LDP series 19x12

LDP series 19x16

The acidity of the carrier of commercial
available reforming catalysts is ranked from
EW series 16x6
least to greatest as follows:
Rib-ring 16x16x6
CaK2Al22O34 < CaAl12O19 < MgAl2O4 < α-Al2O3
Ring 16x10x8
By using more alkaline carrier, carbon
Ring 16x16x6 formation is suppressed very well. Refer to
above rank; CaK2Al22O34 is less acidic than
- 50 100 150 other carrier types. This means ReforMax@ 210
Relative Side crush strength, %
LDP type which is using CaK2Al22O34 as the
carrier has more resistance to carbon
formation comparing to other.

COKE RESISTANCE  How potash works ?

The addition of potassium on the carrier will
The heavier the hydrocarbon feedstock and/or the increase carbon gasification once carbon is
lower the steam to carbon ratio, the more likely formed because it increases adsorption of
carbon is formed on the catalyst. Thermo- water and carbon dioxide at the surface of
dynamically, carbon formation is also favored at catalyst. The carbon gasification reactions are
high temperature. As this occurs, the active sites of as follows:
the catalyst are masked resulting in less reforming,
hence in hotter gas temperatures and more
tendencies to crack. 1) C + 2H2O ==== CO2 + 2H2
2) C + CO2 ==== 2CO

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 4

 The overall accumulation is determined by
difference in the rate of carbon formation and
gasification.
Potassium must be mobile to be effective, but it
is widely known that mobile potassium
significantly reduces the steam reforming
activity. If all the potassium exists in a soluble
form it is more effective at reducing the carbon
formation but there is a great loss of activity.
The soluble potassium is quickly lost from the
catalyst during normal operation and the coking
resistance is lost with the potassium. Water
condensation that usually occurs during startup
and shutdown easily wash potash from the
catalyst. Conversely, if potash is bound too
tightly to the carrier, it will not reduce the
catalyst but it will not be effective towards
suppression of carbon formation.
ReforMax@ 210 LDP is produced with stable
potassium calcium aluminate (CaK2Al22O34)
which is effective at suppressing coking but the
potassium is not too mobile as to reduce the
reforming activity. CaK2Al22O34 releases
potassium in the reformer environment at a
control rate over the lifetime of the catalyst. In
effect, the potassium calcium aluminate acts as
a potassium reserve. The concentration of
potassium in the wet reformed gas is typically
less than 10 pbb.
APPLICATION
Hydrocarbon and steam are reacted on nickel
catalysts resulting in reformed gas comprising of
hydrogen, mixture of carbon oxides and methane
as remaining hydrocarbon. The reactions
represented by methane, is carried out as follows:
CH4 + H2O ==== CO + 3H2 +Q = 49.2 kcal/mol
CO + H2O ==== CO2 + H2 +Q = -9.8 kcal/mol
It is clear that overall reaction is endothermic, and
it is carried out in tubes of the tubular reformers to
ensure that sufficient heat is transferred to the
reacting gas.
Applying for tubular reformer needs to check
typical of feedstock. For the case that the feedstock
and reformer condition has potential to form
carbon deposit, it is usually alkali promoted
reforming catalyst combined with non-promoted
type in application.
In the top or side fired tubular reformer where the
gases flow down to the bottom tube, the top part of
the tubes has much risk carbon formation due to
low temperature as required for reforming reaction
and the feed gas has high hydrocarbon
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
concentration. Based on this, the ReforMax@ 210
LDP as alkali promoted reforming catalyst type is
placed in the top 40 to 60% of the tube. In the
bottom part of the tubes, commonly there is no
heavy hydrocarbon left and the temperature is
adequately to maximize reforming reaction.
Therefore, no potassium is needed at this location
and the catalyst type used is non-promoted type
such as ReforMax@ 330 LDP etc.
No any special pre-treatment used for ReforMax@
210 LDP when put in initial operation. Nickel
oxide will reduce to nickel metal automatically
when rich-hydrogen gas exit upstream reformer
enters. The catalyst could either be left in the
reduced state or be oxidized by steaming (or by
steam and air injection). Oxidation of the catalyst
is preferred when entering to the reactor is
required after the shutdown. Usually, steam used
for the oxidation
POISONS
Low concentrations of certain impurities in feed
gas to the reformer can adversely affect
performance of reforming catalysts. The elements
most often encountered are sulfur, arsenic,
halogens, phosphorus and lead. While some of
these cause permanent damage to the catalyst,
others have only a temporary effect with catalyst
activity returning to normal when the impurity is
removed. In case of permanent poisons, catalyst
replacement is required.
Furthermore, anything introduced to the catalyst,
which blocks physically the catalyst surface
reduces the catalyst activity, like dust, salt and
carbon.
In any case poisoning leads to a more or less
drastic reduction of the catalyst activity resulting
in poor conversion, high tube wall temperature,
carbon accumulation, catalyst breakage and high
pressure drop.
Sulphur - The most common poison for nickel
based reformer catalyst is sulfur. Although the
modern desulphurization systems such as
CoMo/ZnO are capable of lowering sulfur in the
feedstock to negligible levels, upsets still occur.
These upsets can result in significant quantities of
sulphur entering the reformer. The effect of even
small sulphur concentrations in the feed to the
reformer is to dramatically increase the tube-wall
temperatures and methane leakage by imposing a
reduced activity on the catalyst. An example,
increasing sulphur concentration in feed gas from
0.06 to 0.19 ppmv will impose to tube-wall
temperature and methane leakage increase by 5oF
and 0.17% from basis, respectively.
5
As sulphur is not a permanent poison, once it is
removed from the feed, it will come off the catalyst
as H2S and move on down stream. If sulphur
poisoning becomes especially severe, however,
catalyst activity can be affected to the point where
carbon will build up on the catalyst. Under these
conditions, tube-wall temperatures in the
maximum heat flux zone will not return to their
previous values and “hot bands” will be observed in
this zone.
It is recommended that operation of the
desulphurization system should be carefully
controlled to keep the sulphur content in feedstock
less than 0.1 ppmv on a continuous basis,
although levels up to 0.5 ppmv can be tolerated for
a short time.
Chlorine - The effect of chlorine and other halogens
on the reforming catalyst are similar to sulphur.
Chlorine, however, has a much more drastic effect
on the reformer tubes and other plant equipment
as it may lead to stress corrosion. If chlorine is
regularly present in feedstock, it is recommended
that a special chlorine guard catalyst be installed
with the desulphurization system.
Arsenic - Arsenic forms alloy with nickel leading to
irreversible catalyst poisoning. Arsenic present in
the feed in any concentration will accumulate on
the catalyst until it produces the same effects as
sulphur. Arsenic also contaminates the metal of
pipe-work and reformer tubes, which must be
carefully cleaned to avoid further poisoning of fresh
catalyst.
Other poisons - Impurities such as copper, lead,
iron, phosphate, etc will accumulate at the top of
reformer tubes and affect catalyst performance due
to lowering catalyst activity by blocking active site.
This effect is non-reversible, therefore, if necessary,
the contaminated catalyst can be replaced by an
equivalent volume of new catalyst.
Carbon deposit - Carbon deposits, which in most
cases, are caused by severe sulphur poisoning or
accidental operation of a hot reformer on feed gas
with low or no steam mixed in. As mentioned
above, carbon can be formed by either thermal
cracking of hydrocarbon or CO disproportion
(Boudouard reaction):
CH4 ==== C + 2H2 (thermal cracking)
2CO ==== C + CO2 (CO disproportion)
Cracking reaction occurs at the acidic sites and is
thermodynamically favored at high temperature
and is a cause of most carbon formation in fired
reformers. CO disproportion reaction is favored at
high CO partial pressures and low temperatures.
These conditions are uncommon in most tubular
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
reformers as the gas temperature is high enough.
Heavier hydrocarbons in the feed will crack first.
As this occurs, the active sites of the catalyst are
masked resulting in less reforming, hence in
hotter gas temperatures and more tendencies to
crack.
The formation and accumulation of carbon on the
catalyst, basically, is controlled by reaction
kinetics. During normal operation, the rate of
carbon removal is much greater that the rate of
carbon formation and therefore there is no carbon
accumulation. The rate of carbon formation
increases with heavier feedstock, lower steam to
carbon ratio, and higher gas temperatures. When
the rate of carbon formation exceeds the rate of
removal, accumulation of carbon on the catalyst
reduces activity and void fraction resulting in:
 Poor conversion
 Increased tube-wall temperatures
 Catalyst breakage, and

Increased pressure drop.
Process upsets that lead to cracking reactions
include; loss of steam, temperature excursions,
feed composition changes, and catalyst poisoning.
The higher the operating pressure the more
favorable the carbon formation. To prevent carbon
formation a minimum steam to carbon ratio has
to be maintained. Besides steam, also CO2 can
suppress carbon formation. The effect, however, of
CO2 is approximately only half of the one of
steam.
TECHNICAL SERVICES
Clariant Group firmly believes that even an
outstanding catalyst may not provide the best
performance without the appropriate level of
assistance during the phases of selection,
installation, start-up and operation. Within our
Technical Service Group, we have a wide range of
personnel with specific expertise in the areas of
catalyst characterization, research, catalyst
installation, start-up, plant operation, and
performance evaluations.
This depth of knowledge allows us to provide the
following services such as:
6
 ▪ Review of reactor system design
▪ Selection of proper catalyst
▪ Technical reviews of start-up/shutdown
procedures
Technical assistance for loading, catalyst
▪ start-up and shutdown
Routine performance evaluations
▪ Trouble shooting
▪ Catalyst life projections
▪ Chemical and physical analyses of spent
catalyst
▪

GUARANTEES
Clariant grants to the user process performance
guarantees covering the performance of its
ReforMax@ 210 LDP catalyst. Before granting such
performance guarantees, the design conditions
and/or anticipated operating conditions must be
reviewed and guarantees will be given based upon
Clariant’s design kinetic system.

SHIPPING INFORMATION
Shipments are made in steel drums with the
standard capacity of 200 and/or 208 liter per
drum.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 7

 Product Bulletin

Issue, April 2014

PUBLISHER
PT. CLARIANT KUJANG CATALYSTS
CONTACT
For further information or
support, please contact
sales@clariant-kujang.com

Catalyst for
FIRED HYDROCARBON REFORMING
 Catalyst for
Fired Hydrocarbon Reforming
ReforMax@ 330 LDP

CONTENT

General ............................................................................................................................. 1

Product features................................................................................................................ 1

Applications ...................................................................................................................... 4

Poisons ............................................................................................................................. 5

Technical services ............................................................................................................. 6

Guarantees ....................................................................................................................... 6

Shipping information ........................................................................................................ 6

What is precious to you?

 GENERAL
The hydrocarbon steam reforming process is the
principal industrial process used to manufacture
synthesis gas for the production of hydrogen,
ammonia and methanol. The heart of this process
is the tubular steam reformer where the
hydrocarbon feed plus steam is catalytically
reacted to produce the synthesis gas. In ammonia
plant, tubular steam reformer that usually called
primary reforming is followed by an adiabatic
hydrocarbon reforming process i.e. secondary
reformer to finalized methane reforming and air
injection as nitrogen source for ammonia
production. Meanwhile in modern methanol plant,
it is followed by an adiabatic hydrocarbon
reforming process i.e. auto-thermal reformer
where high purity oxygen fed to finalized methane
reforming as specified.

The Clariant Group (fomerly: Süd-Chemie) has

manufactured the fired hydrocarbon reforming
catalysts over 50 years, providing a complete
range of the catalyst such that selection can be
made of the most effective catalyst for any
condition of process feed and process design. The
products, which in all forms contains nickel as
active metal has been developed continuously to
respond users desire where they favor to choice
the catalysts that having characteristic of high
activity, low pressure drop, high physical strength
and more resistance to poison.

ReforMax@ 330 LDP is one of fired hydrocarbon

reforming catalyst produced by Clariant that is
used in light to medium fired and adiabatic
hydrocarbon reforming. The original name is G-90
LDP. The original name is G-90 LDP. Replacing
product name was done in line with Clariant’s
simplifying product nomenclature in order for the
customer to more easily recognize the products
and their usage.

PRODUCT FEATURES
ReforMax@ 330 LDP is the product type that has
excellent in low pressure drop and high geometric
surface area comparing to another types. It has
two standard sizes i.e. 19x16 mm and 19x12 mm.
The catalyst has gray appearance, no odor,
insoluble in water and melting point is more than
1900oC. It is negligible fire and explosion hazards
when exposed to heat or flame by reaction with
incompatible substances.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 1

The catalyst performance in a fired or tubular
steam-hydrocarbon reformer cannot be discussed
in terms, which would be generally applicable to all
reformers. Most users equate performance with life
as manifested by catalyst strength. This is due to
the fact, that the vast majority of reformers are
designed so conservatively that virtually any
reforming catalyst will demonstrate satisfactory
performance as long as the catalyst remains
physically intact. Some of the more modern high
severity reformers are much less conservative in
design and as a result localized catalyst activity
becomes the limiting feature of the catalyst, as high
activity must be maintained to maintain tube skin
temperatures within allowable limits. Even in
furnaces where localized activity is a major criteria,
strength may be become the limiting factor as some
very active catalyst demonstrate very poor strength
characteristics with the result that when the
catalyst loses physical integrity, premature catalyst
change-outs due to physical or strength
considerations.
ReforMax@ 330 LDP visualization
Typical properties of ReforMax® 330 LDP
Nominal Content, wt% ReforMax® 330 LDP
Nickel Oxide 14
Carrier, Ca-Aluminate Balance
Shape 10 Holed Ring
Size, mm 19x12; 19x16
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
CATALYST SHAPE
With respect to surface area, it is evident that the
simplest and most effective way to maximize
catalyst activity is by using catalyst particles with
highest external geometric surface area. At first
this was accomplished by using smaller size rings
on the expense, however, of increasing pressure
drop. A breakthrough came in 1978 when Sud-
Chemie (now: Clariant Group) developed the first
high geometric surface shape, a seven-spoked
wheel, which provides approx. 60 percent higher
activity compared to the standard ring. This
seven-spoked wheel shape is called EW shape,
standing for enhanced wheel.
The Clariant Group always was the leading
company in developing more sophisticated shapes
comprising maximum geometric surface area
while at the same time featuring low pressure
drop. The latest product shape development is the
LDP shape. LDP stands for low differential
pressure. As it is the case for EW shape, the LDP
shape comprises high geometric surface area,
thus high activity for the steam reforming
reaction. The most striking feature, however, of
the LDP shape is the combination of high activity
with extremely low pressure drop.
ACTIVITY
Catalyst activity is determined by surface area
and active metal content. High activity means
faster reaction rate will be occurred. Relating to
tubular reformer, the activity also affects tube
wall temperature; depend on sections of the tube.
 Surface area:
In the tubular reformer, gas diffusion into the
catalyst pores is the essential step for overall
reaction rate. Almost of the reaction takes
place on the outer surface of the catalyst
particle. Thus, higher activity will be achieved
for the catalyst with higher surface area.
LDP series 19x12
LDP series 19x16
EW series 16x6
Rib-ring 16x16x6
Ring 16x10x8
Ring 16x16x6
- 50 100 150 200
Relative GSA, %
2
 Nickel content:
Nickel (Ni) is catalytically active component of
any commercially available steam reforming
catalyst. Therefore, one can assume that
increasing content of nickel will also increase
the catalyst activity. This is true only to a
certain extent. The optimum nickel content is
around 14 to 18 %-wt as Ni.
40
35
Reaction
30 rate
x 1000
25
20
15
10
5
0 The initial pressure drop is determined by the
4 8 121620 24
Nickel content, %-wt
 Tube wall temperature:
Tube costs are a significant item in the overall
economics of a reforming plant and it is good
practice to operate the reformer with the tube
wall temperatures as low as possible consistent,
of course, with satisfactory reformed gas quality.
Even a slight increase in the tube wall
temperatures will have a drastic impact on the
tube life. When the maximum tube wall
temperature is increased by only 10oC it may
result in an up to 30 percent shortened lifetime
of the reformers tube.
The effect of the catalyst activity on the tube
wall temperature can vary significant with
furnace design and operation and requires for
an understanding a closer look to the
relationship between activity and heat transfer.
The heat transfer from outer surface of tube to
the center of the catalyst is represented by the
equation as follows: Q/A = U (TOW – TG), where;
Q/A: heat flux
U: overall heat transfer coefficient
TOW: outer surface of tube temperature
TG: gas inside tube temperature
About 70 percent of the heat flux is used in the
reforming reaction and remaining is for the
sensible heat. In sections of the tube where the
reaction is far away from reforming equilibrium,
a more active catalyst can achieve more
endothermic reforming and will hence consume
a larger part of the incoming heat which will
result in a lower gas temperature in that region.
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
This will allow the same amount of heat input
starting with a cooler outer tube wall
temperature.
However, in regions of the tube where the gas
already close to the reforming equilibrium, a
more active catalyst cannot achieve additional
reforming and there will be little effect on the
temperature of the gas and of the outer tube
wall in that section
PRESSURE DROP
Everything related to pressure drop is most
critical in the operation of the tubular reformer.
One has to consider both, the initial pressure
drop and the evolution of the pressure drop with
time on stream.
 Initial pressure drop:
catalyst shape and to a certain extent by the
loading method. Laboratory test shows
pressure drop of ReforMax@ 330 LDP is much
lower than other types. This means loading
ReforMax@ 330 LDP type allows running higher
throughput rate at the same pressure drop to
other types.
 Time on stream pressure drop:
The catalyst loaded in the reformer tubes is
subject to extreme physical stress due to the
expansion and compression of the tubes
during plant start-up, shutdown and upset
conditions. High crush strength is necessary to
prevent catalyst breakage due to those
problems. The carrier of catalyst composition
has important effect to build catalyst that
having high crush strength. The Clariant
Research Group has found hibonite type
carrier that also known as CaAl12O19 which is
the only irreversible formed phase in the
CaO/Al2O3 phase diagram. This is the reason
for the extreme stability over physical and
thermal stresses of reforming catalysts that
using this carrier type. The ReforMax@ 330 LDP
catalyst uses hibonite carrier type and has
much higher crush strength than other types
▪ What’s more dominant ?
As long as extreme physical stress can be
avoided even if during plant start-up,
shutdown or upset conditions; then
breakage of catalyst would be hindered and
pressure drop across catalyst bed is
primarily determined by catalyst shape.
3
 LDP series 19x12 APPLICATION
LDP series 19x16 Hydrocarbon and steam are reacted on nickel
catalysts resulting in reformed gas comprising of
EW series 16x6
hydrogen, mixture of carbon oxides and methane
as remaining hydrocarbon. The reactions,
Rib-ring 16x16x6
represented by methane, are carried out as
follows:
Ring 16x10x8

Ring 16x16x6
CH4 + H2O ==== CO + 3H2 +Q = 49.2 kcal/mol
CO + H2O ==== CO2 + H2 +Q = -9.8 kcal/mol
- 50 100 150

Relative Pressure drop, % It is clear that overall reaction is endothermic and

it is carried out in tubes of the tubular reformers
to ensure that sufficient heat is transferred to the
reacting gas.
LDP series 19x12

LDP series 19x16 In an adiabatic reformer, i.e. secondary and auto-

thermal reformers, the reaction is performed in an
EW series 16x6 adiabatic catalytic reactor, which reduces the
residual methane to a specified level under the
Rib-ring 16x16x6 reactions as mentioned above. The methane exit is
usually very low, because of equilibrium at
Ring 16x10x8 temperatures higher than are obtained in
upstream reformer, i.e. fired or tubular reformer.
Ring 16x16x6

- 50 100 150 Heat required for an adiabatic reforming is

generated by reaction of the oxygen with some of
Relative Side crush strength, % the hydrogen, which produced in upstream
reformer. This reaction occurred mainly in the
mixing or burning zone above catalyst;

COKE RESISTANCE
The heavier the hydrocarbon feedstock and/or the
lower the steam to carbon ratio, the more likely
carbon is formed on the catalyst. Thermo-
dynamically, carbon formation is also favored at
high temperature. As this occurs, the active sites of
the catalyst are masked resulting in less reforming,
hence in hotter gas temperatures and more
tendencies to crack.
2H2 + O2 ---- 2O +Q = -115.6 kcal/mol
For secondary at ammonia plant, the air to carbon
ratio is fixed by the nitrogen to hydrogen ratio
required for the ammonia synthesis loop. Mean-
while, in autothermal reforming at methanol plant
that usually used high purity oxygen, the
requirement of oxygen is to be ensured that all
oxygen incoming was finished burning that no
enter to the methanol synthesis loop.

It is well understood that the acidic sites of the

catalyst carrier promote the carbon formation. The
acidity of the carrier of commercial available
reforming catalysts is ranked from least to greatest
as follows:
CaAl12O19 < MgAl2O4 < α-Al2O3
By using more alkaline carrier, carbon formation is
suppressed very well. Refer to above rank;
CaAl12O19 is less acidic than α-Al2O3. This means,
as previous describing, ReforMax@ 330 LDP type
used CaAl12O19 carrier is more resistance to carbon
formation comparing to other reforming catalyst
types that used α-Al2O3 carrier type.
ReforMax@ 330 LDP used in both tubular and
autothermic reformers. Applying for tubular
reformer needs to check typical of feedstock. The
catalyst is normally used for light to heavy natural
gas both at low to high steam to carbon ratio. For
the case that the feedstock has potential to form
carbon deposit, it is usually combined with alkali
based reforming catalyst in application. For
autothermic reformers, ReforMax@ 330 LDP is
loaded beneath heat shield layer, as main
reforming catalyst. The catalyst requirement
ranges from 80 to 90 percent of total catalyst
volume, which is remaining is heat shield catalyst.

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 4

No any special pre-treatment used for ReforMax@
330 LDP when put in initial operation. Nickel oxide
will reduce to nickel metal automatically when rich-
hydrogen gas exit upstream reformer enters. The
catalyst could either be left in the reduced state or
be oxidized by steaming (or by steam and air
injection). Oxidation of the catalyst is preferred
when entering to the reactor is required after the
shutdown. Usually, steam used for the oxidation.
POISONS
Low concentrations of certain impurities in feed gas
to the reformer can adversely affect performance of
reforming catalysts. The elements most often
encountered are sulfur, arsenic, halogens,
phosphorus and lead. While some of these cause
permanent damage to the catalyst, others have only
a temporary effect with catalyst activity returning to
normal when the impurity is removed. In case of
permanent poisons, catalyst replacement is
required.
Furthermore, anything introduced to the catalyst,
which blocks physically the catalyst surface
reduces the catalyst activity, like dust, salt and
carbon.
In any case poisoning leads to a more or less
drastic reduction of the catalyst activity resulting in
poor conversion, high tube wall temperature,
carbon accumulation, catalyst breakage and high
pressure drop.
Sulphur - The most common poison for nickel
based reformer catalyst is sulfur. Although the
modern desulphurization systems such as
CoMo/ZnO are capable of lowering sulfur in the
feedstock to negligible levels, upsets still occur.
These upsets can result in significant quantities of
sulphur entering the reformer. The effect of even
small sulphur concentrations in the feed to the
reformer is to dramatically increase the tube-wall
temperatures and methane leakage by imposing a
reduced activity on the catalyst. An example,
increasing sulphur concentration in feed gas from
0.06 to 0.19 ppmv will impose to tube-wall
temperature and methane leakage increase by 5oF
and 0.17% from basis, respectively.
As sulphur is not a permanent poison, once it is
removed from the feed, it will come off the catalyst
as H2S and move on down stream. If sulphur
poisoning becomes especially severe, however,
catalyst activity can be affected to the point where
carbon will build up on the catalyst. Under these
conditions, tube-wall temperatures in the
maximum heat flux zone will not return to their
previous values and “hot bands” will be observed in
this zone.
PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group
It is recommended that operation of the
desulphurization system should be carefully
controlled to keep the sulphur content in
feedstock less than 0.1 ppmv on a continuous
basis, although levels up to 0.5 ppmv can be
tolerated for a short time.
Chlorine - The effect of chlorine and other
halogens on the reforming catalyst are similar to
sulphur. Chlorine, however, has a much more
drastic effect on the reformer tubes and other
plant equipment as it may lead to stress
corrosion. If chlorine is regularly present in
feedstock, it is recommended that a special
chlorine guard catalyst be installed with the
desulphurization system.
Arsenic - Arsenic forms alloy with nickel leading
to irreversible catalyst poisoning. Arsenic present
in the feed in any concentration will accumulate
on the catalyst until it produces the same effects
as sulphur. Arsenic also contaminates the metal
of pipe-work and reformer tubes, which must be
carefully cleaned to avoid further poisoning of
fresh catalyst.
Other poisons - Impurities such as copper, lead,
iron, phosphate, etc will accumulate at the top of
reformer tubes and affect catalyst performance
due to lowering catalyst activity by blocking active
site. This effect is non-reversible, therefore, if
necessary, the contaminated catalyst can be
replaced by an equivalent volume of new catalyst.
Carbon deposit - Carbon deposits, which in most
cases, are caused by severe sulphur poisoning or
accidental operation of a hot reformer on feed gas
with low or no steam mixed in. As mentioned
above, carbon can be formed by either thermal
cracking of hydrocarbon or CO disproportion
(Boudouard reaction):
CH4 ==== C + 2H2 (thermal cracking)
2CO ==== C + CO2 (CO disproportion)
Cracking reaction occurs at the acidic sites and is
thermodynamically favored at high temperature
and is a cause of most carbon formation in fired
reformers. CO disproportion reaction is favored at
high CO partial pressures and low temperatures.
These conditions are uncommon in most tubular
reformers as the gas temperature is high enough.
Heavier hydrocarbons in the feed will crack first.
As this occurs, the active sites of the catalyst are
masked resulting in less reforming, hence in
hotter gas temperatures and more tendencies to
crack.
5
The formation and accumulation of carbon on the
catalyst, basically, is controlled by reaction
kinetics. During normal operation, the rate of
carbon removal is much greater that the rate of
carbon formation and therefore there is no carbon
accumulation. The rate of carbon formation
increases with heavier feedstock, lower steam to
carbon ratio, and higher gas temperatures. When
the rate of carbon formation exceeds the rate of
removal, accumulation of carbon on the catalyst
reduces activity and void fraction resulting in:
GUARANTEES
Clariant grants to the user process performance
guarantees covering the performance of its
ReforMax@ 330 LDP catalyst. Before granting such
performance guarantees, the design conditions
and/or anticipated operating conditions must be
reviewed and guarantees will be given based upon
Clariant’s design kinetic system.



Poor conversion SHIPPING INFORMATION
Increased tube-wall temperatures
 Catalyst breakage, and
 Shipments are made in steel drums with the
Increased pressure drop.
standard capacity of 200 and/or 208 liter per
drum.
Process upsets that lead to cracking reactions
include; loss of steam, temperature excursions,
feed composition changes, and catalyst poisoning.

The higher the operating pressure the more

favorable the carbon formation. To prevent carbon
formation a minimum steam to carbon ratio has to
be maintained. Besides steam, also CO2 can
suppress carbon formation. The effect, however, of
CO2 is approximately only half of the one of steam.

TECHNICAL SERVICES
Clariant Group firmly believes that even an
outstanding catalyst may not provide the best
performance without the appropriate level of
assistance during the phases of selection,
installation, start-up and operation. Within our
Technical Service Group, we have a wide range of
personnel with specific expertise in the areas of
catalyst characterization, research, catalyst
installation, start-up, plant operation, and
performance evaluations.

This depth of knowledge allows us to provide the

following services such as:

▪ Review of reactor system design

▪ Selection of proper catalyst
▪ Technical reviews of start-up/shutdown
procedures
Technical assistance for loading, catalyst
▪ start-up and shutdown
Routine performance evaluations
▪ Trouble shooting
▪ Catalyst life projections
▪ Chemical and physical analyses of spent
catalyst
▪

PT. CLARIANT KUJANG CATALYSTS – Member of CLARIANT Group 6