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High Performance GEAR Catalyst for Sulfuric Acid

Plants.

GEAR Series

*NEW PRODUCTS*

The new catalysts designated as GR-330 and GR-310 include an optimized shape and
enhanced formula providing for interchangeable use in all passes of the converter. GR330 is produced in a 13 mm diameter size while GR-310 is 12 mm in diameter.

G = Geometrically Optimized
E = Enhanced Surface Area
A = Activity Improvement
R = Reduced Pressure Drop

Energy Savings and Extended Operating Time


The unique hexa-lobe ring shape of the GEAR catalyst improves the catalyst spacing in
the bed (less nesting of the catalyst), which allows for more dust to be held throughout
the bed. The optimized shape provides reduced pressure drop which saves energy by
lowering duty of the blower. The GEAR catalyst will lengthen the time necessary for

the main compressor to reach its capacity, thus increasing the operating time between
scheduled turnarounds.

Lower SO2 Emissions and Increased Acid Production


The hexa-lobed ring GEAR shape was engineered to provide improved activity. The
shape, a result of extensive laboratory research, provides better access for the SO2 and O2
gases to the active sites on the surface and within the catalyst.

When gas strength remains constant, GEAR catalyst meets emissions equal to XLP
catalyst but with 5-10% less volume.

Less volume = smaller converter = reduced capital cost

When catalyst volume is the same as XLP catalyst, improved activity in GEAR catalyst
means:

Up to 25% lower emissions, or

Up to 15% increase in plant capacity

For even lower emissions, use SCX-2000 in Pass 4.

GEAR catalyst design options custom-designed for your needs!

Use GR-330 Catalyst throughout converter for lowest pressure drop and
maximum extension in production cycle.

Use GR-310 Catalyst throughout converter for highest conversion performance


and extension in production cycle.

Use a GR-330/GR-310 Catalyst Mix in converter for a significant improvement in


conversion, reduction in pressure drop and extension in production cycle.

Haldor Topsoe
Sulfuric Acid
Whether producing sulfuric acid directly from spent acid, elemental sulfur or sulfur
compound containing gasses, we have the optimal solution. Our high activity catalysts
ensure high energy efficiency, low pressure-drop and production stability, as well as an
exceptionally long life. When integrated into our proven and flexible processes they
ensure our customers achieve higher production rates, improved heat recovery, optimal
energy-efficiency and the lowest possible SO2 emissions.

Applications within this area

Sulfur Dioxide Oxidation(active tab)

Wet Gas Sulfuric Acid (WSA)

Sulfur Dioxide Oxidation


Catalysts
The performance catalysts we supply for this application are listed below.

VK-WSX

VK-WSA

VK-WL

VK-WH

VK-701 LEAP5

VK-69

VK-59

VK-48 (daisy)

VK-48 (cylinder)

VK-38 (ring)

VK-38 (daisy)

VK-38 (cylinder)

Equipment
The proprietary equipment we supply for this application are listed below.

Waste Heat Boiler (Sulfuric Acid)

VK-38 (daisy)

The VK38 formulation provides excellent activity over a wide range of operating
conditions. VK38 is the only catalyst on the market that can be used effectively in all
beds of any SO2 converter. For continuous operation VK38 offers a broad temperature
range of 400-630C (750-1170F) and can withstand repeated temperature spikes up to
650C (1200F). VK38 is designed to initiate the reaction at a temperature as low as
360C (680F), ensuring a smooth plant start-up, minimising pre-heat time due to its
superior catalyst activity.

12 mm Daisy
Improved energy efficiency throughout the operating cycle due to low initial pressure
drop; 25 mm Daisy dust protection catalyst with 100% longer on-stream time compared
to the 12 mm Daisy in dusty feed gases; 6 mm cylinder and 10 mm ring: ensure an even
gas distribution in applications with very low velocity converters.
The 12 mm Daisy has become the most widely used catalyst shape on the market since
introduced by Topse in 1984. The high void fraction results in improved energy
efficiency throughout the operating cycle due to low initial pressure drop and increased
capacity for dust. Topses 12 mm Daisy-shape has proven to be robust as well, with
reported screening losses typically well below 10%. Topses VK38, VK48, and VK59
formulations are all available in the 12 mm Daisy-shape. Benefits

low initial pressure drop

high dust capacity yielding in a lower rate of pressure drop increase

high activity

low screening losses

25 mm Daisy
New improved dust protection catalyst. For catalyst beds suffering from rapid pressure
drop increase due to dust in the feed gas, a top layer of Topses 25 mm Daisy-shape
catalyst can provide a cost effective remedy. The extra void fraction and a lower specific
surface area allow a significantly higher capacity for dust, distributing it throughout a
larger volume of the catalyst bed. The result is a lower rate of pressure drop increase
providing improved energy efficiency and longer intervals between catalyst screenings.
Benefits

30-50% longer on-stream time compared to existing ring-shaped dust-protection


catalysts

100% longer on-stream time compared to 12 mm Daisy

maintenance cost savings due to less frequent catalyst screening

energy cost savings due to lower plant pressure drop

production increase due to longer time at maximum rate before pressure drop
forces production delay

The sensitivity to plugging and pressure drop build-up in a catalyst bed depends on the
bed void and how the dust is distributed. The penetration depth increases with the size of
the catalyst particles because the specific surface area is lower. Topse has developed a
new, improved dust protection catalyst in the shape of a large 25 mm Daisy. This new
super Daisy catalyst combines the effect of a larger void fraction for higher dust capacity
and the effect of a lower specific surface area for improved dust distribution. Installation
of a 10-15 cm (4-6 inches) top layer in the 1st bed results in 30-35% longer production
campaigns when compared with 20 mm rings, or a doubling when compared with 12 mm
Daisy. Yet catalytic activity and mechanical strength are the same as for the classical 20
mm rings.

Development of a new dust protection catalyst


The desire to prolong production campaigns in sulphuric acid plants even beyond the
possibilities offered with the 20 mm ring-shaped dust protection catalyst set the goals for
development of a new improved Topse catalyst product. As a starting point, the model
described above was validated against industrial experience for existing catalysts, for
which good agreement between the model and industrial measurements of pressure drop
development for the 1st bed was found. The rapid increase of pressure drop over the top
15 cm (6 inches) of a 6 mm cylindrical catalyst operating at high dust concentration is
due to the high specific surface area and low initial void of the 6 mm pellets. The
delaying of pressure drop increase observed for 10 mm rings and more pronounced for
the 12 mm Daisy is primarily caused by their higher initial void fraction. For larger
pellets such as the 20 mm ring, the dust penetrates deeper into the bed, thus, postponing
pressure drop build-up even further. The 90% and 55% longer production campaigns
calculated for the 20 mm ring compared to the 10 mm ring and the 12 mm Daisy,
respectively, are confirmed by feedback from more than 60 industrial installations of the
20 mm ring. A number of new improved catalyst sizes and shapes were subsequently
evaluated by the model, and it was found that a new 25 mm Daisy in an excellent way
combines the advantages of a large sized pellet and a high-voidage shape. The initial
pressure drop is a bit higher due to the extra 10 cm catalyst but as the dust accumulates,
the 25 mm Daisy shows its superior dust capacity enabling 30-35% longer production
campaigns when compared with 20 mm rings or a doubling when compared with 12 mm
Daisy. The typical dust loading capacity per m2 reactor cross section, before the pressure
drop reaches a critical limit, is around 10 kg/m2 for the 12 mm Daisy, 16 kg/m2 for the
20 mm ring, and 20 kg/m2 for the new 25 mm Daisy. The manufacture of the 25 mm
Daisy was finally demonstrated and optimised in a full-scale production in our factory.
Compared to the 20 mm ring, the new dust protection catalyst has the same catalytic
activity and mechanical strength measured by side crush strength, drop test and attrition
loss as the 20 mm ring, however, the initial pressure drop is 25-30% lower. This new
product is now ready for industrial installation.
Property
Composition
Shape

Value
V2O5/K/Na
Daisy

VK-38 (ring)
The VK38 formulation provides excellent activity over a wide range of operating
conditions. VK38 is the only catalyst on the market that can be used effectively in all
beds of any SO2 converter. For continuous operation VK38 offers a broad temperature
range of 400-630C (750-1170F) and can withstand repeated temperature spikes up to
650C (1200F). VK38 is designed to initiate the reaction at a temperature as low as
360C (680F), ensuring a smooth plant start-up, minimising pre-heat time due to its
superior catalyst activity.

12 mm Daisy improved energy efficiency throughout the operating cycle due to low
initial pressure drop; 25 mm Daisy dust protection catalyst with 100% longer on-stream
time compared to the 12 mm Daisy in dusty feed gases; 6 mm cylinder and 10 mm ring:
ensure an even gas distribution in applications with very low velocity converters.
Property
Composition
Shape

Value
V2O5/K/Na
Ring

VK-38 (cylinder)
The VK38 formulation provides excellent activity over a wide range of operating
conditions. VK38 is the only catalyst on the market that can be used effectively in all
beds of any SO2 converter. For continuous operation VK38 offers a broad temperature
range of 400-630C (750-1170F) and can withstand repeated temperature spikes up to
650C (1200F). VK38 is designed to initiate the reaction at a temperature as low as
360C (680F), ensuring a smooth plant start-up, minimising pre-heat time due to its
superior catalyst activity.
Property
Composition
Shape

Value
V2O5/K/Na
Cylinder

VK-48 (daisy)

VK48 is a high vanadium version of the standard all-round VK38 catalyst.The catalyst
composition is specifically formulated for lower pass service, particularly where the
process gas contains large amounts of SO3. The conversion ratio of SO2 affects the
balance between the active vanadium species in the catalyst. An optimised ratio of the
alkali-metal promoters enables an increased vanadium content in VK48, resulting in a
considerably enhanced activity. In high SO3 gas environments, such as the lower passes

of single absorption plants, or the third pass of a 3:1 double absorption plant, VK48 offers
a significant performance advantage.
12 mm Daisy improved energy efficiency throughout the operating cycle due to low
initial pressure drop; 6 mm cylinder and 10 mm ring: ensure an even gas distribution in
applications with low gas velocity converters.
Property
Composition
Shape

Value
V2O5/K/Na
Daisy

VK-48 (cylinder)
VK48 is a high vanadium version of the standard all-round VK38 catalyst.The catalyst
composition is specifically formulated for lower pass service, particularly where the
process gas contains large amounts of SO3. The conversion ratio of SO2 affects the
balance between the active vanadium species in the catalyst. An optimised ratio of the
alkali-metal promoters enables an increased vanadium content in VK48, resulting in a
considerably enhanced activity. In high SO3 gas environments, such as the lower passes
of single absorption plants, or the third pass of a 3:1 double absorption plant, VK48 offers
a significant performance advantage.
Property
Composition
Shape

Value
V2O5/K/Na
Cylinder

VK-59

VK59 is a caesium-promoted catalyst optimised for medium to high strength SO2 gasses
with continuous operation down to 370C (700F). A top layer of VK59 in the first pass
makes it possible to accommodate high strength SO2 feed gas without exceeding the
maximum outlet temperature of 630C (1165F) and still maintain high bed conversion
efficiency. VK59 installed in the lower pass(es) of single absorption plants allows for
significant conversion improvement.
Benefits

accommodates strong SO2 feed gas without excessive first pass exit temperatures

greatly improved operating fl exibility for rapidly changing feed gas composition

low ignition temperature for faster and cleaner start-ups

significantly extended idle time for autothermal restarts

improved overall conversion in single absorption plants Improved energy


efficiency throughout the operating cycle due to low initial pressure drop.

Low ignition temperature


VK59 and VK69 have an exceptionally low ignition or strike temperatures of 320330C (610-625F) that offer new possibilities for faster and cleaner start-ups.
Autothermal restarts can be accomplished after a significantly longer idle time without
the use of pre-heat.

12 mm Daisy
The 12 mm Daisy has become the most widely used catalyst shape on the market since
introduced by Topse in 1984. The high void fraction results in improved energy
efficiency throughout the operating cycle due to low initial pressure drop and increased
capacity for dust. Topses 12 mm Daisy-shape has proven to be robust as well, with
reported screening losses typically well below 10%. Topses VK38, VK48, and VK59
formulations are all available in the 12 mm Daisy-shape.
Benefits

low initial pressure drop

high dust capacity yielding in a lower rate of pressure drop increase

high activity

low screening losses

Property
Composition
Shape

Value
V2O5/K/Na/Cs
Daisy

VK-69

VK69 is designed specifically for the final pass(es) of double absorption plants. In the
lean SO2 gas environment after the inter-pass absorption tower, the unique VK69

formulation offers unmatched high activity throughout the entire operating temperature
range. This affords existing plants the opportunity to greatly reduce SO2 emissions and/or
increase production rates. For new or revamped plants, SO2 emissions of under 50 ppm
are possible. Using caesium as a promoter, VK69s extremely low ignition or strike
temperature will significantly reduce pre-heat time and improve start-up performance.
VK69 is manufactured in a unique 9 mm Daisy-shape. The high surface area contributes
to the high activity in this gas environment and the high void-fraction ensures a low
pressure drop and good dust tolerance.
Benefits

possibility for over 50% reduction in SO2 emission from existing double
absorption plants

possibility for signifi cantly increased production without increasing SO2


emissions

less than 50 ppm of SO2 emissions possible from new or revamped plantslow
ignition temperature for faster and cleaner start-ups

long lifetime and low screening losses industrially proven since 1996

Low ignition temperature


VK59 and VK69 have an exceptionally low ignition or strike temperatures of 320330C (610-625F) that offer new possibilities for faster and cleaner start-ups.
Autothermal restarts can be accomplished after a significantly longer idle time without
the use of pre-heat.

9 mm Daisy
VK69 is produced in the unique 9 mm Daisy-shape. In the low SO2 environment, after
the intermediate absorption tower, the 9 mm size and Daisy-shape combination gives
30% extra activity compared to a 12 mm Daisy-shape, in part due to the higher surface
area. Also, the Daisy-shape ensures remarkably low pressure drop. The high surface area
of the 9 mm Daisy contributes to the high activity, and the high void fraction ensures a
low pressure drop.
Property
Composition
Shape

Value
V2O5/K/Na/Cs
Daisy

BASF catalyst of SO2 to SO3


Introduction
In 1901, Badische Anilin- & Soda-Fabrik (BASF) was issued German Patents 113933 and 133933
which described their pioneering activities in the development of the contact process which
employed a catalyst to promote the oxidation of SO 2 and O2 to give SO3. At this time the active
ingredient in the catalyst was platinum. Platinum catalysts exhibit high activity but were costly
and were easily deactivated by poisons such as arsenic trioxide (As 2O3).
Development continued into alternative catalysts that did not suffer the disadvantages of platinum
and were less costly to manufacture. In 1913, BASF was issued German Patent 291792 and
Swiss Patent 71326 for a catalyst consisting of vanadium pentoxide and alkali metal oxides on a
porous silica carrier. This new catalyst was first used in a commercial scale plant in 1915. The
results were successful and the remaining platinum catalysts was soon replaced with vanadium
pentoxide catalyst.
Today, BASF offer 3 different types of catalyst in a variety of shapes for various situations in
sulphuric acid plants.
Catalyst Types
The physical properties of the catalyst are provided in the following table and a brief description of
each catalyst is given below.

04-110

Shapes

V2O5 Content

S6: 6 mm pellet
S8: 8 mm pellet
SS11x4: 11 x 4 mm
star ring
SR10x5: 10 x 5 ring
SR11x4: 11x 4 ring

04-111

S6: 6 mm pellet
S8: 8 mm pellet
SS11x4: 11 x 4 mm
star ring
SR10x5: 10 x 5 ring
SR11x4: 11x 4 ring

04-115

SR10x5: 10 x 5 ring
SS11x4: 11 x 4 mm
star ring

6 wt%

8 wt%

600 kg/m

550 kg/m

5.5

Operating
Temperature

400 to 600C
(752 to 1112F)
depending on gas
composition

415 to 630C
(779 to 1166F)
depending on gas
composition

Ignition Temperature

minimum 360C
(680F)
depending on gas
composition

minimum 380C
(716F)
depending on gas
composition

Bulk Density - Pellets

04-110
Type 04-110 is a proven catalyst primarily used in the first converter bed. The catalyst is suitable
for sulphur combustion gases and for waste gases from metallurgical plants or from H 2S
combustion (i.e. wet catalysis). The catalyst possesses a low ignition temperature of 380 oC which
is useful during initial plant start-ups. Normal inlet temperatures are in the range of 410 to 430 oC.
Maximum operating temperature is 630oC which makes it suitable for treating gases containing
up to 13% SO2.
04-111
Type 04-111 is a highly active catalyst for use in catalyst beds after the first bed. The higher
activity results in closer approaches to the thermodynamic equilibrium. Ignition temperatures can
be as low as 360oC depending on the gas composition. Maximum operating temperatures are
limited to 600oC.
04-115
Type 04-115 is a caesium based catalyst which allows normal inlet temperature down to 370 to
385oC depending on gas composition. The catalyst can be used as an ignition layer in the first
pass or in the final pass. The lower inlet temperatures allow gases containing up to 16% SO 2
without thermally overloading the subsequent beds. The ignition temperature of the catalyst is
about 340oC with a maximum operating temperature of 630oC.