Introduction
Product features
Application
Poisons
Technical services
Guarantees
Shipping information
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INTRODUCTION PRODUCT FEATURES
The hydrocarbon steam reforming process is the Similar to ReforMax@ 330 LDP type, ReforMax@
principal industrial process used to manufacture 210 LDP is the product type that has excellent in
synthesis gas for the production of hydrogen, low pressure drop and high geometric surface
ammonia and methanol. The heart of this process area comparing to another types. The different
is the tubular steam reformer where the between these catalysts is the ReforMax@ 210
hydrocarbon feed plus steam is catalytically reacted LDP type is promoted with potassium for coke
to produce the synthesis gas. In ammonia plant, resistance improvement. It allows using the
tubular steam reformer that usually called primary catalyst for heavier hydrocarbon and LPG
reforming is followed by an autothermic reforming feedstock. The catalyst has two standard sizes i.e.
process i.e. secondary reformer to finalized 19x16 mm and 19x12 mm. It has gray
methane reforming and air injection as nitrogen appearance, no odor, insoluble in water and
source for ammonia production. Meanwhile in melting point is more than 1900oC. It is negligible
modern methanol plant, it is followed by auto- fire and explosion hazards when exposed to heat
thermal reformer where high purity oxygen fed to or flame by reaction with incompatible
finalized methane reforming as specified. substances.
Sd-Chemie Group has manufactured the The catalyst performance in a tubular steam-
hydrocarbon reforming catalysts over 50 years, hydrocarbon reformer cannot be discussed in
providing a complete range of the catalyst such that terms, which would be generally applicable to all
selection can be made of the most effective catalyst reformers. Most users equate performance with
for any condition of process feed and process life as manifested by catalyst strength. This is due
design. The products, which in all forms contains to the fact, that the vast majority of reformers are
nickel as active metal has been developed designed so conservatively that virtually any
continuously to respond users desire where they reforming catalyst will demonstrate satisfactory
favor to choice the catalysts that having performance as long as the catalyst remains
characteristic of high activity, low pressure drop, physically intact. Some of the more modern high
high physical strength and more resistance to severity reformers are much less conservative in
poison. Sd-Chemie Group also has developed design and as a result localized catalyst activity
nickel based hydrocarbon reforming catalysts becomes the limiting feature of the catalyst, as
contain potassium which is fully incorporated into high activity must be maintained to maintain tube
the catalyst carrier to minimize the formation of skin temperatures within allowable limits. Even in
carbon. This allows using widely range of feedstock furnaces where localized activity is a major
for hydrocarbon steam reforming, such as light to criteria, strength may be become the limiting
heavy hydrocarbon, LPG and naphtha. factor as some very active catalyst demonstrate
very poor strength characteristics with the result
ReforMax@ 210 LDP is one of potassium promoted that when the catalyst loses physical integrity,
hydrocarbon reforming catalyst produced by Sd- premature catalyst change-outs due to physical or
Chemie that is used for reforming light to heavy strength considerations.
hydrocarbon and LPG feedstock in hydrocarbon-
steam tubular reformer. The original name is G-91 ReforMax@ 210 LDP visualization
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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Typical properties of ReforMax 210 LDP
LDP series 19x12
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relationship between activity and heat transfer. Time on stream pressure drop:
The heat transfer from outer surface of tube to The catalyst loaded in the reformer tubes is
the center of the catalyst is represented by the subject to extreme physical stress due to the
equation as follows: Q/A = U (TOW TG), where; expansion and compression of the tubes
Q/A: heat flux during plant start-up, shutdown and upset
U: overall heat transfer coefficient conditions. High crush strength is necessary to
TOW: outer surface of tube temperature prevent catalyst breakage due to those
TG: gas inside tube temperature problems. The carrier of catalyst composition
has important effect to build catalyst that
About 70 percent of the heat flux is used in the having high crush strength. Sd-Chemie
reforming reaction and remaining is for the Research Group has found hibonite type
sensible heat. In sections of the tube where the carrier that also known as CaAl12O19 which is
reaction is far away from reforming equilibrium, the only irreversible formed phase in the
a more active catalyst can achieve more CaO/Al2O3 phase diagram. This is the reason
endothermic reforming and will hence consume for the extreme stability over physical and
a larger part of the incoming heat which will thermal stresses of reforming catalysts that
result in a lower gas temperature in that region. using this carrier type. The ReforMax@210
This will allow the same amount of heat input LDP catalyst uses hibonite carrier type which
starting with a cooler outer tube wall is incorporated with potassium oxide (K2O) for
temperature. coke resistance. Similar to ReforMax@ 330
However, in regions of the tube where the gas LDP type, the catalyst has much higher crush
already close to the reforming equilibrium, a strength than other types.
more active catalyst cannot achieve additional
reforming and there will be little effect on the
temperature of the gas and of the outer tube LDP series 19x12
wall in that section.
LDP series 19x16
- 50 100 150
Whats more dominant?
Relative Pressure drop, % As long as extreme physical stress can be
avoided even if during plant start-up, shutdown or
upset conditions; then breakage of catalyst would
Pressure drop be hindered and pressure drop across catalyst
Everything related to pressure drop is most critical bed is primarily determined by catalyst shape.
in the operation of the tubular reformer. One has to
consider both, the initial pressure drop and the
Coke resistance
evolution of the pressure drop with time on stream.
The heavier the hydrocarbon feedstock and/or the
lower the steam to carbon ratio, the more likely
Initial pressure drop:
carbon is formed on the catalyst.
The initial pressure drop is determined by the
Thermodynamically, carbon formation is also
catalyst shape and to a certain extent by the
favored at high temperature. As this occurs, the
loading method. Laboratory test shows pressure
active sites of the catalyst are masked resulting in
drop of ReforMax@ 210 LDP is much lower than
less reforming, hence in hotter gas temperatures
other types. This means loading ReforMax@ 210
and more tendencies to crack.
LDP type allows running higher throughput rate
at the same pressure drop to other types.
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Carbon formation reactions: The overall accumulation is determined by
The carbon can be formed under the reactions difference in the rate of carbon formation and
as follows: gasification.
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In the top or side fired tubular reformer where the can result in significant quantities of sulphur
gases flow down to the bottom tube, the top part of entering the reformer. The effect of even small
the tubes has much risk carbon formation due to sulphur concentrations in the feed to the reformer
low temperature as required for reforming reaction is to dramatically increase the tube-wall
and the feed gas has high hydrocarbon temperatures and methane leakage by imposing a
concentration. Based on this, the ReforMax@ 210 reduced activity on the catalyst. An example,
LDP as alkali promoted reforming catalyst type is increasing sulphur concentration in feed gas from
placed in the top 40 to 60% of the tube. In the 0.06 to 0.19 ppmv will impose to tube-wall
bottom part of the tubes, commonly there is no temperature and methane leakage increase by
heavy hydrocarbon left and the temperature is 5oF and 0.17% from basis, respectively.
adequately to maximize reforming reaction.
Therefore, no potassium is needed at this location As sulphur is not a permanent poison, once it is
and the catalyst type used is non-promoted type removed from the feed, it will come off the catalyst
such as ReforMax@ 330 LDP etc. as H2S and move on down stream. If sulphur
poisoning becomes especially severe, however,
No any special pre-treatment used for ReforMax@ catalyst activity can be affected to the point where
210 LDP when put in initial operation. Nickel oxide carbon will build up on the catalyst. Under these
will reduce to nickel metal automatically when rich- conditions, tube-wall temperatures in the
hydrogen gas exit upstream reformer enters. The maximum heat flux zone will not return to their
catalyst could either be left in the reduced state or previous values and hot bands will be observed
be oxidized by steaming (or by steam and air in this zone.
injection). Oxidation of the catalyst is preferred
when entering to the reactor is required after the It is recommended that operation of the
shutdown. Usually, steam used for the oxidation. 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
POISONS for a short time.
Low concentrations of certain impurities in feed gas Chlorine
to the reformer can adversely affect performance of The effect of chlorine and other halogens on the
reforming catalysts. The elements most often reforming catalyst are similar to sulphur. Chlorine,
encountered are sulfur, arsenic, halogens, however, has a much more drastic effect on the
phosphorus and lead. While some of these cause reformer tubes and other plant equipment as it
permanent damage to the catalyst, others have may lead to stress corrosion. If chlorine is
only a temporary effect with catalyst activity regularly present in feedstock, it is recommended
returning to normal when the impurity is removed. that a special chlorine guard catalyst be installed
In case of permanent poisons, catalyst replacement with the desulphurization system.
is required.
Arsenic
Furthermore, anything introduced to the catalyst, Arsenic forms alloy with nickel leading to
which blocks physically the catalyst surface irreversible catalyst poisoning. Arsenic present in
reduces the catalyst activity, like dust, salt and the feed in any concentration will accumulate on
carbon. the catalyst until it produces the same effects as
sulphur. Arsenic also contaminates the metal of
In any case poisoning leads to a more or less pipe-work and reformer tubes, which must be
drastic reduction of the catalyst activity resulting in carefully cleaned to avoid further poisoning of
poor conversion, high tube wall temperature, fresh catalyst.
carbon accumulation, catalyst breakage and high
pressure drop. Other poisons
Impurities such as copper, lead, iron, phosphate,
Sulphur etc will accumulate at the top of reformer tubes
The most common poison for nickel based reformer and affect catalyst performance due to lowering
catalyst is sulfur. Although the modern catalyst activity by blocking active site. This effect
desulphurization systems such as CoMo/ZnO are is non-reversible, therefore, if necessary, the
capable of lowering sulfur in the feedstock to contaminated catalyst can be replaced by an
negligible levels, upsets still occur. These upsets equivalent volume of new catalyst.
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Carbon deposit
Carbon deposits, which in most cases, are caused
TECHNICAL SERVICES
by severe sulphur poisoning or accidental operation
of a hot reformer on feed gas with low or no steam Sd-Chemie Group firmly believes that even an
mixed in. As mentioned above, carbon can be outstanding catalyst may not provide the best
formed by either thermal cracking of hydrocarbon performance without the appropriate level of
or CO disproportion (Boudouard reaction): assistance during the phases of selection,
installation, start-up and operation. Within our
CH4 ==== C + 2H2 (thermal cracking) Technical Service Group, we have a wide range
2CO ==== C + CO2 (CO disproportion) of personnel with specific expertise in the areas of
catalyst characterization, research, catalyst
Cracking reaction occurs at the acidic sites and is installation, start-up, plant operation, and
thermodynamically favored at high temperature and performance evaluations.
is a cause of most carbon formation in fired
reformers. CO disproportion reaction is favored at This depth of knowledge allows us to provide the
high CO partial pressures and low temperatures. following services such as:
These conditions are uncommon in most tubular
reformers as the gas temperature is high enough.
Heavier hydrocarbons in the feed will crack first. As Review of reactor system design
this occurs, the active sites of the catalyst are Selection of proper catalyst
masked resulting in less reforming, hence in hotter Technical reviews of start-up/shutdown
gas temperatures and more tendencies to crack. procedures
Technical assistance for loading, catalyst
The formation and accumulation of carbon on the start-up and shutdown
catalyst, basically, is controlled by reaction kinetics. Routine performance evaluations
During normal operation, the rate of carbon Trouble shooting
removal is much greater that the rate of carbon Catalyst life projections
formation and therefore there is no carbon Chemical and physical analyses of spent
accumulation. The rate of carbon formation catalyst
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
Poor conversion Sd-Chemie grants to the user process
Increased tube-wall temperatures performance guarantees covering the
Catalyst breakage, and performance of its ReforMax@ 210 LDP catalysts.
Increased pressure drop. Before granting such performance guarantees,
the design conditions and/or anticipated operating
Process upsets that lead to cracking reactions conditions must be reviewed and guarantees will
include; loss of steam, temperature excursions, be given based upon Sd-Chemies design kinetic
feed composition changes, and catalyst poisoning. system.
The higher the operating pressure the more
favorable the carbon formation. To prevent carbon
formation a minimum steam to carbon ratio has to SHIPPING INFORMATION
be maintained. Besides steam, also CO2 can
suppress carbon formation. The effect, however, of Shipments are made in steel drums with the
CO2 is approximately only half of the one of steam. standard capacity of 200 and/or 208 liter per
drum.
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