Product Bulletin

Hydrocarbon Reforming Catalyst

ReforMax@ 210 LDP
CONTENT

Introduction

Product features

Application

Poisons

Technical services

Guarantees

Shipping information

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INTRODUCTION
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.
Sd-Chemie Group has manufactured the
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. Sd-Chemie Group also has developed
nickel based 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
hydrocarbon reforming catalyst produced by Sd-
Chemie 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
Sd-Chemies simplifying product nomenclature in
order for the customer to more easily recognize the
products and their usage.
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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
Typical properties of ReforMax 210 LDP
LDP series 19x12

Nominal Content, ReforMax 210 LDP LDP series 19x16

wt%:
EW series 16x6
Nickel Oxide 18 Rib-ring 16x16x6
Potassium Oxide 1.5
Ring 16x10x8
Carrier Calcium-Aluminate
Ring 16x16x6
Shape 10 Holed Ring
- 50 100 150 200
Size, mm 19 x 16; 19 x 12
Relative GSA, %

Catalyst shape Nickel content:

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 Sd-Chemie
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
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 rate x 1000

called EW shape, standing for enhanced wheel. 30

Sd-Chemie 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.
25
20
15
10
5
0
4 8 12 16 20 24
Nickel content, %-w t
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

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 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.
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.
LDP series 19x12
LDP series 19x16
EW series 16x6
Rib-ring 16x16x6
Ring 16x10x8
Ring 16x16x6
- 50 100 150
Relative Pressure drop, %
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:
The initial pressure drop is determined by the
catalyst shape and to a certain extent by the
loading method. Laboratory test shows 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.
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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. Sd-Chemie
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@210
LDP catalyst uses hibonite carrier type which
is incorporated with potassium oxide (K2O) for
coke resistance. Similar to ReforMax@ 330
LDP type, the catalyst has much higher crush
strength than other types.
LDP series 19x12
LDP series 19x16
EW series 16x6
Rib-ring 16x16x6
Ring 16x10x8
Ring 16x16x6
- 50 100 150
Relative Side crush strength, %
Whats 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.
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.
Thermodynamically, 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.
 Carbon formation reactions:
The carbon can be formed under the reactions
as follows:
1) Thermal or catalytic cracking:
CH4 ==== C + 2H2
2) Boudouard reaction or CO disproportion:
2CO ==== C + CO2
3) CO reduction:
CO + H2 ==== C + H2O
4) Reverse water-shift reaction:
CO2 + 2H2 ==== C + 2H2O
Carbon formation from CO is 3 to 10 times
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.
Carrier or support:
Resulting carbon will deposit on catalyst surface
causes deactivated catalyst, catalyst break-up
and catalyst overheating. The suppression of
carbon formation reactions is accomplished by
decreasing the acidity of the catalyst by
incorporating alkaline earth metals into the
carrier and by further promoting with an alkali
metal. The most common commercial
combinations used are potassium promoted
calcium aluminate and potassium promoted
magnesium aluminate. The combination retards
the formation of carbon and also accelerates the
carbon gasification reaction once it has been
formed.
The acidity of the carrier of commercial available
reforming catalysts is ranked from least to
greatest as follows:
CaK2Al22O34 < CaAl12O19 < MgAl2O4 < -Al2O3
By using more alkaline carrier, carbon formation
is suppressed very well. Refer to above rank;
CaK2Al22O34 is less acidic than other carrier
types. This means ReforMax@ 210 LDP type
which is using CaK2Al22O34 as the carrier has
more resistance to carbon formation comparing
to other.
How potash works?
The addition of potassium on the carrier will
increase carbon gasification once carbon is
formed because it increases adsorption of water
and carbon dioxide at the surface of catalyst.
The carbon gasification reactions are as follows:
5) C + 2H2O ==== CO2 + 2H2
6) C + CO2 ==== 2CO
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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
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
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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.
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.
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.
SD-CHEMIE
TECHNICAL SERVICES
Sd-Chemie 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
GUARANTEES
Sd-Chemie grants to the user process
performance guarantees covering the
performance of its ReforMax@ 210 LDP catalysts.
Before granting such performance guarantees,
the design conditions and/or anticipated operating
conditions must be reviewed and guarantees will
be given based upon Sd-Chemies design kinetic
system.
SHIPPING INFORMATION
Shipments are made in steel drums with the
standard capacity of 200 and/or 208 liter per
drum.