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MAXIMISING

PYGAS
OPERATIONS
PRODUCTIVITY
YUZOH SATOH, CLARIANT, JAPAN,
STEFAN BREJC, AND PAIGE MARIE
MORSE, CLARIANT, GERMANY, AND
IAN BUTTRIDGE AND JOSEPH GENTRY,
GTC TECHNOLOGY, USA, OUTLINE THE
RECENT CATALYST AND EQUIPMENT
DEVELOPMENTS CAPABLE
OF MAXIMISING PYGAS
OPERATIONS PRODUCTIVITY.

P
yrolysis gasoline is a common byproduct The first stage converts diolefins (or dienes)
in the production of ethylene, particularly primarily, but also removes acetylenes and styrene
when heavier feeds are used. This mixture, by selective hydrogenation. Effective conversion in
typically referred to as pygas, has many this stage is critical to downstream operations,
reactive components and impurities that make it enabling such processing benefits as:
unsuitable for gasoline blending or other purposes nn Improved oxygen stability and colour.
without further treatment. After full hydro nn Reduced gum content.
treatment and desulfurisation, the pygas can be nn Reduced fouling in the downstream hydro
upgraded into valuable petrochemical feedstocks desulfurisation unit.
such as benzene, toluene, and xylenes. OleMax 600 is a high performance palladium
The raw pygas from the cracker has high based catalyst for this first stage hydrogenation. It
potential for gum formation, in addition to existing uses a spherical alumina carrier and exhibits very high
gums, which creates a significant challenge in activity and excellent physical durability. Clariant has
processing. The hydrotreatment process is highly a long history of expertise in selective hydrogenation
exothermic so careful selection of equipment and technology, building from predecessor company
catalyst can have a major impact on the reliability of Süd-Chemie.
operations. Recent commercial operations using OleMax 600 is particularly effective at reducing
OleMax® 600 catalyst from Clariant with a newly styrene levels and gum formation in first stage
designed distributor, developed by GTC Technology, processing. The formation of insoluble gums is a
has demonstrated very stable operations for first particular concern, as it is the primary reason for
stage diene hydrogenation with a much more catalyst deactivation. This catalyst can be used in
uniform temperature profile and longer operating single or double bed systems.
lifetime than other systems. In the single bed system, typical operations
Pyrolysis gasoline contains hydrocarbons chains combine heavy gasoline from the quench tower and
of C5 and higher and with varying levels of light gasoline from the debutaniser bottoms. The
saturation. Processing proceeds in two stages: feed is pumped to reactor pressure, mixed with
diolefin removal, followed by olefin and sulfur recycle and then introduced to the reactor.
removal. Hydrogen is added to the reactor to maintain system
pressure. Part of the reactor effluent is cooled and recycled to the directed to a Claus unit for sulfur recovery. The condensed vapour
feed, to limit the temperature rise and vaporisation across the product and the balance of cooled liquid reactor effluent are fed
catalyst bed. to a depentaniser or directly to the second stage pygas
The vapour fraction of the reactor effluent is cooled and hydrotreater unit. It is challenging to maintain styrene conversion
condensed. The vent containing the excess hydrogen can be used above 90% per pass in the single bed system.
as a hydrogen source for the second stage hydrotreater, or may be The two bed design is used for large scale reactors when higher
diene and styrene conversion are required. Two configurations are
common in the dual bed system. One process configuration
recycles most of the reactor effluent back to the feed as a top
dilution, which limits the temperature rise and the vaporisation
across the catalyst bed.
The other configuration option uses an additional side quench
that recycles product to the second bed also, as shown in Figure 1.
As the top bed is more exposed to feed contaminants, it can be
replaced more frequently than the bottom catalyst bed.
GTC Technology has invented a much improved distributor
design that enables even and efficient mixing of the feed to the
catalyst beds, and thus much more stable and efficient operations.
The distributor is designed to distribute the liquid evenly across the
tower cross section, while maximising the number of drip points.
Figure 1. Pyrolysis gasoline 1st stage (two bed Figure 2 shows a simplified diagram of distributor operations, and
system). illustrates the benefits of a drip point multiplying effect. It is
important to note that physical constraints often do not allow a
large amount of drip points or risers in conventional arrangement.
The GTC distributor combines unique drip point design and
placement to achieve minimal cross sectional temperature variance,
and greater operational stability.1 Operations with this distributor
design have four to seven times higher effective drip point density,
without excessively small holes, than typical designs and can
achieve an effective drip point density of 200 - 300/m2.

Figure 2. Increased drip points in the distributor


provide improved liquid spreading and much
better catalyst coverage.

Figure 4. Top bed temperature profile for first


few months of operation, with the GTC distributor
Figure 3. Stable temperatures achieved across and with alternate equipment. NOTE: Same
both reactor beds using only top recycle. temperature and height scales used for both
charts.

HYDROCARBON
Reprinted from September 2013 ENGINEERING
GTC uses a modified Moore-Rikovena method to evaluate the nn The distributor must be assembled in parts with a bolted
geometry of each distributor. This method has been used in removable construction.
distillation columns to calculate the distribution quality (DQ) of any nn In some large reactors, the required support beams also distort
given design as a fractional percentage, with 100% reflecting the the ideal pattern.
ideal design. The primary drip point will be completed using an An optimised design will minimise the effect of these issues as
equilateral triangular pitch. However some issues prevent a perfect much as possible, and the DQ calculation can be used to evaluate
flow pattern, as noted below: each design. An optimised layout enables distribution quality
nn The reactor is round, thus at the periphery the pitch will be approaching 90%. The efficiency of operation is further enhanced
slightly distorted, and spacing to the reactor wall can cause by the use of a mixer between the reactor beds. This mixer collects
dead areas. and redistributes the liquid from the upper bed and mixes it with
any quench feed. The liquid from the top reactor bed and the
quench is brought into a central distribution point, mixed, and then
sent to the distributor below. This process ensures that the lower
bed achieves maximum performance, and also that any issues with
the upper bed caused by catalyst deactivation or hot spots do not
propagate down to the second bed. This is achieved with minimal
reactor volume.
The OleMax 600 catalyst has excellent activity and stability
and well balanced physical properties, which combine to increase
cycle length without any process modifications. With the addition
of the GTC distributor to the equipment, even longer cycle length
is possible with further optimised temperature control.
The advantages of this catalyst system and distributor design
are illustrated by results from commercial operations at an existing
processing unit. The feedstock for this unit is raw pyrolysis gasoline
and the unit was operated with a gradual inlet temperature
increase to prevent leakage of outlet diene values and styrene
levels. Diene values are maintained well below the target and
styrene levels are less than 0.2 wt%.
The reactor demonstrated excellent temperature stability with
minimal increase required after more than 200 days of service, as
shown in Figure 3. The performance shows notable improvement
over the previous catalyst and distributor specified by the original
licensor of this unit, confirming superior catalyst stability and
improved feed distribution.
This reactor stability is maintained throughout the run, as
Figure 5. Bottom bed temperature profile for first shown in Figures 4 and 5. The temperature profiles across the top
few months of operation with the GTC distributor
and bottom beds, respectively, at one, two and three months of
and with alternate equipment. NOTE: same
temperature and height scales used for both operation reflect only a gradual increase across the period. This
charts. contrasts with the previous system for this unit that exhibits a
much less stable temperature profile.
One key performance advantage from the combined
operation of OleMax 600 with the GT-599 distributor is the
significant resistance to gum content in the feed. Based on
current performance, the operating lifetime of the catalyst is
approximately 25% longer when compared to previous
operations without the GTC distributor. The expected
performance improvement is illustrated in Figure 6, showing
estimated cycle length improvement correlated with gum
content in the feed.
Overall, the system utilising the new distributor from GTC with
the OleMax 600 catalyst enables more stable operations with
uniform temperature profile and longer operating lifetime. The
value of this performance has been further verified with the recent
selection of this system by two new customers.

References
1. MOORE, F., and RUKOVENA, F., ‘Liquid and Gas Distribution in
Figure 6. Projected performance using GTC Commercial Packed Towers’, 36th Canadian Chemical Engineering
distributor with OleMax 600 catalyst. Conference, October 5 - 8, 1986 Paper 23b.
2. OleMax is a registered trademark of Clariant.

HYDROCARBON
ENGINEERING Reprinted from September 2013
Clariant international ltd
Rothausstrasse 61
4132 Muttenz
Switzerland

Catalysts
petrochemicals@clariant.com

www.Catalysts.Clariant.Com

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