COURIER NO. 33 Art.

More performance out of your isomerization unit?

Industrial examples on the benefit of improved catalysts
By M. de Boer, C. Johnson

SUMMARY

Isomerization units in refineries or petrochemical complexes are used to convert low octane
C5/C6 streams into high-octane products and to produce i-C4 for alkylation or MTBE. An
increasing number of refiners are faced with a bottleneck in an isomerization unit, not in the
last place because of new benzene legislation. Application of improved catalysts proves to
be a cost-effective way to de-bottleneck an isomerization unit and achieve longer life cycles.
At this moment seven customers are taking benefit of AT-2/AT-2G isomerization catalysts.

INTRODUCTION

The installed capacity for isomerization technology amounts to about 1,500 thousand bpsd,
and is growing steadily. The market for paraffin isomerization technology is dominated by
UOP with Penex (C5/C6) and Butamer (C4) units. Nowadays, the majority of the isomerization
units are based on amorphous catalysts (platinum on chlorided alumina), which typically yield
4 points higher RON than the less active zeolite-based catalysts. Technology in the market
for butane isomerization is completely based on amorphous catalysts. As of January 1996, a
C4-isomerization capacity of 187 thousand BPSD was installed worldwide, and many more
units have been announced.2

The market for isomerization technology and catalysts is still growing. Planned expansions
will lead to an annual growth of about 5% for the next five years. The incentive for the growth
is found in:
• Increasing demand for octane barrels in countries outside Europe and North America
• Increasing demand for isobutane for the production of alkylate and MTBE
• And legislative pressure on the benzene content in gasoline

The first two aspects directly lead to a higher demand for products from isomerization units.
The pressure on benzene levels in gasoline has grown in the past few years. Whereas the
current typical benzene level amounts to 2.3 vol% in Europe, the maximum benzene level in
the E.U. will be 1.0 vol% as per January 1st 2000. Led by developments in the USA, the Reid
vapor pressure limits are also under pressure in Europe.5 This asks for less blending of the
volatile, but high octane (iso)butane, and more octane out of the less volatile C5/C6 fraction,
which can be accomplished by skeletal isomerization.

A commonly applied solution to the benzene problem is to raise the Initial Boiling Point (IBP)
of the reformer feed, thereby feeding more benzene, naphthenes and C7+ to the
isomerization unit. This will lead to greater required isomerization capacities and increased
severity. A refinery equipped with a reformer and an isomerization unit will therefore optimize
the feed cut point in the naphtha splitter in order to comply with legislation, while still
producing maximum octane barrels.

At the same time, many refiners and MTBE producers attempt to boost the capacity of
butane isomerization units in order to make more isobutane for alkylate production (a clean,
high octane contribution to the gasoline pool) or for MTBE synthesis. In the volatile market of
MTBE, an enhanced flexibility in production capacity can be a (competitive) advantage.

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COURIER NO. 33 Art. 6

Improved catalysts

Akzo Nobel and TOTAL have together developed improved catalysts for the isomerization of
butane and light naphtha, as currently applied in several third-party isomerization units and
within the TOTAL organization. A new family of Akzo Nobel Catalysts has emerged, denoted
Akzo Nobel Total-2 or AT-2. As this type of catalyst can both be used for the isomerization of
C4 and for C5/C6, two separate grades were developed: AT-2 for C4 and AT-2G for C5/C6
isomerization. The use of AT-2 in C4 isomerization units (often as a part of an MTBE
complex) has been licensed together with ABB Lummus Global.

AT-2 was applied for the first time in a butane isomerization unit as part of a world-scale
MTBE production facility in Dubai (licensed by ABB Lummus Global). As the catalyst showed
to be by far the most active catalyst available in this market segment, other customers
followed soon. In the meanwhile, five major oil companies have tested the catalyst and all of
them confirmed the claims that AT-2 and AT-2G are (at least) 30 and 40% more active than
any other commercially available isomerization catalyst. A new production facility to de-
bottleneck the manufacturing of AT-2 and AT-2G was started-up in the first quarter of 1998.

AT-2 and AT-2G are catalysts for C4 and for C5/C6 isomerization respectively. Both grades
are amorphous, bifunctional catalysts, consisting of platinum on chlorided alumina. The most
important reactions taking place in C4 and C5/C6 paraffin isomerization are collected in figure
1. Skeletal rearrangement of small paraffins is limited by thermodynamics. Low temperatures
favor the equilibrium, which asks for catalysts providing higher activity. The typical operating
range of amorphous catalysts in butane isomerization is between 130° and 200°C and space
velocities between 2 and 6 hr-1. Isobutane yields between 55% and 65% can be obtained on
a once-through basis. An incentive to use catalysts with a high activity (low temperature) is
the reduction of hydrocracking reactions stimulated by high a temperature, which lead to
yield loss.

Figure 1

Hydrocarbon reactions in C4 and C5/C6-isomerization

n-C4 i-C4 skeletal isomerization Desired reaction limited by thermodynamics;
high catalyst activity improves i-C4 yield;
C4

usual i-C4 yield around 60%

hydrocracking Hydrocracking gives yield loss; high Rx T
exacerbates this reaction

n-C5 i-C5 Desired reactions limited by thermodynamics;

skeletal isomerization
• usual i-C5 ratio (%) in mid-70s
• 2,2 DMB formation is rate-limiting
3 MP

High catalyst activity improves the i-C5 and i-

2,3 DMB C6 yield due to low temperature operation
C5/C6

n-C6
2,2 DMB
2 MP
Benzene saturation very exothermic; occurs
benzene saturation on hydrogenation function

hydrocracking Hydrocracking of C5 and C6 leads to yield

loss; high Rx T exacerbates this reaction

hydrodecyclization / ring opening Hydrodecyclization of naphthenes (MCP, CH)

favored by high Rx T and high catalyst activity

hydrocracking Hydrocracking of C7+ leads to yield loss; high

Rx T exacerbates this reaction

The number of components in C5/C6 operation is only a little more extensive. The skeletal
isomerization of n-C5 into i-C5 yields only one branched isomer (neopentane formation is
negligible). The equilibrium concentration of isopentane is in the mid-seventies (percent)
under normal operating conditions (between 110° and 200°C). Isomerization of normal
hexane leads to 4 isomers, of which 2,3-DMB possesses the highest-octane contribution.
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COURIER NO. 33 Art. 6

The formation of 2,2-DMB is rate limiting in the reaction sequence. The use of AT-2G gives
conversion to branched paraffins close to thermodynamic equilibrium, and liquid yields are
typically 99+ %.

Apart from skeletal isomerization, ring opening of naphthenes takes place. As mentioned
earlier, the presence and concentration of benzene precursors depends on the operation of
the refinery in general and specifically on the IBP chosen for the reformer feed. Heavy
components (C7+) can be processed and all benzene is rapidly saturated to cyclohexane on
AT-2G.

The industrial use of AT-2 and AT-2G (7 commercial references and growing) are
demonstrated in three examples: (A) debottlenecking a Butamer or Penex unit by the use of
AT-2(G), (B) compliance with future benzene legislation, and (C) catalyst lifetime extension.

Example A:
De-bottleneck your isomerization unit

Various economic circumstances bear an incentive to raise the throughput of an

isomerization unit, such as, a higher demand of alkylate gasoline or MTBE (C4
isomerization), or an increased demand of low benzene, high-octane isomerate (C5/C6
isomerization).

Table 1 gives a comparison between the operation of a C4-isomerization unit using a generic,
amorphous catalyst and AT-2. The throughput can be raised by 40% at equal product quality
(isobutane ratio: iC4 / (iC4 + nC4)). At equal throughput the isobutane ratio will be several
percent points higher per pass.

Table 1: De-bottlenecking a C4-isomerization unit

Base case Improved case

Unit throughput (bpsd) 13,000 18,000 (+ 40%)
Product quality Base Base
Catalyst Reference AT-2
Catalyst loaded weight Base Base - 8 %

The economic benefit of the improved case depends on the value attributed to isobutane or
MTBE for C4-isomerization or octane barrels in C5/C6 isomerization; however, the application
of an improved catalyst is definitely the most cost-effective way to de-bottleneck a unit.
Alternatively, a refiner can use the improved catalyst to reduce costs at equal unit
performance by short loading one or two reactors. Two industrial cases have demonstrated
the feasibility of this concept: proportional shortloading with a more active catalyst gave the
same unit performance.

Example B:
Use your isomerization unit to comply with benzene legislation

Present legislation in the USA and upcoming legislation in the European Union will force
refiners to produce gasoline with 1.0 vol% benzene maximum. Although many solutions to
this problem exist, the most frequently cited option is raising the IBP of the reformer feed. As
typically 80% of the benzene in the gasoline pool originates from reformate this is the most
logical solution. Thus, a larger fraction of the benzene precursors (methylcyclopentane and
cyclohexane) will end up in the isomerization feed.

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COURIER NO. 33 Art. 6

Figure 2

Reformer IBP

Base +2 AT
-2(
Isomerization G)

(R+M)/2
Re
fe ren
ce

Base
Base Base +20
Naphtha splitter Reformer
wt% Bz precursors
in Isom feed

Figure 2 gives the impact of the concentration of benzene precursors in the isomerization
feed on the isomerate octane (expressed as (R+M)/2). Upon increasing the content of
benzene precursors in the isomerization feed the octane of the isomerate will come down.
This is due to the reversible (Langmuir) adsorption of naphthenes on the catalyst, which
inhibits the skeletal isomerization of paraffins. The loss of catalyst activity can be made up by
the use of an improved catalyst. Typicals for this case are given in table 2.

Table 2: Use your isomerization unit to comply with benzene legislation

Base case Improved case

Unit throughput (bpsd) 10,000 10,000
Feed quality (wt. Bz precursors) Base +10 Base +10
Isomerate (R+M)/2 Base -0.8 Base
Catalyst Reference AT-2G

Example C:
Catalyst life extension

In general Chloride alumina isomerization catalysts are more susceptible to contaminants

like water (precursors) than zeolite based isomerization catalysts; this drawback is more than
compensated for by the better octane yields. Also in this respect, AT-2 and AT-2G comprise
a step improvement over other commercially available catalysts.

Chlorided alumina catalysts are irreversibly deactivated by water or precursors thereof (CO,
CO2, methanol, etc.). This is due to the reaction of water with the chlorided alumina catalyst,
yielding HCl and a hydroxylated catalyst surface. Although all Butamer and Penex units are
equipped with dryers to remove water (precursors), it is inevitable that traces of moisture will
enter the reactor. Sub-ppm traces of moisture are enough to slowly eat away the catalyst
activity. The sensitivity to moisture of this kind of catalysts is presented in figure 3, in which
chlorided alumina catalysts (AT-2(G) and a reference) are titrated with water under realistic
conditions. The experiments show that it takes 50% more water to completely deactivate AT-
2(G) than the reference catalyst.

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COURIER NO. 33 Art. 6

Figure 3

Isomerization activity
AT
-2(
G)
Re
fer
en
c e

1.0 1.5

kg water dosed / 100 kg catalyst

The implications for catalyst longevity are summarized in table 3. Since water (precursors) is
the dominating cause of catalyst deactivation, the enhanced resistance to water can be
directly translated into catalyst longevity. A 50% improvement of catalyst life can thus be
obtained.

Table 3: Extend the catalyst lifetime

Base case Improved case

Catalyst Reference AT-2(G)
Kg water needed to kill 100 kg catalyst 1.0 1.5
Predicted lifetime Base Base * 1.5

As an example of the very stable operation of AT-2 in an industrial application, the results of
three years operation in a butane isomerization unit (as part of a world-scale MTBE complex
in Dubai (UAE), engineering and licensing by ABB Lummus Global) are shown in figure 4.

Figure 4 shows the Weighed Average Bed Temperature (WABT) for 60% conversion to
isobutane (in only one on-line reactor) as a function of time on stream. The curve shows that
only some 6°C deactivation has protruded in three years time. With an end-of-life WABT of
some 190-200°C (outlet 205-210°C), the catalyst still has a long time to go.

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COURIER NO. 33 Art. 6

Figure 4

165

160

155

WABT (°C)
150

145

140 Data: Dugas (Dubai, U.A.E.)

135
Normalized WABT (60% isobutane)
130
0 200 400 600 800 1000
TOS (d)

CONCLUSIONS

Three examples using AT-2 and AT-2G have demonstrated that it is possible to improve the
performance of an isomerization unit. There are several options for the refiner: one can 1)
use less catalyst, 2) raise the unit throughput, 3) process heavier feed (more naphthenes,
benzene, C7+), 4) increase catalyst life, and/or 5) operate the unit at lower temperature for
improved conversion.

The benefit for the AT-2(G) user depends on the situation (1–5). In option 1, using less
catalyst (e.g., 25% less) will lead to a proportional decrease of the fill costs compared to a
full load. In 4, -extending catalyst life by 50%- the next catalyst change-out date will be
pushed back and cost saving will be in the future.

The user of AT-2(G) catalyst can make extra profit when scenario 2 applies, because more
octane barrels (or isobutane) will be produced. If an octane barrel is worth US$0.25, a 25%
increase in throughput in a 10,000 BPSD Penex unit will bring more than US$3 million per
year extra. Scenario 3 applies when low-benzene gasoline limits the operability of the
reformer, as demonstrated in case B. As for scenario 5, the unit can be operated at a
thermodynamically favored, lower temperature.

REFERENCES

1. T.C.M. Lidderdale, Fuel Technology & Management, March/April 1996, p. 47

2. OGJ Special, Oil & Gas Journal (October, 13 1997)
3. M. de Boer, P.J. Nat, E. H. van Broekhoven, 1997 NPRA Annual Meeting (March 16-18,
1997), San Antonio, paper AM-97-55, and M. de Boer, P.J. Nat, E.H. van Broekhoven:
Worldwide Industry Conference Solid Acid/Base ’97 (New Orleans)
4. L.F. Albright: Worldwide Industry Conference Solid Acid/Base ’97 (New Orleans); A.
Gardner, Today’s Refinery (November 1997), 21
5. HP Impact, Hydrocarbon Processing, July 1997, p. 27

Figure 1:The most important reactions in C4 and C5/C6 isomerization

Figure 2: Impact of benzene precursor concentration on the isomerate octane
Figure 3: Impact of water on the activity of chlorided alumina catalysts
Figure 4 Performance of AT-2 in an industrial butane isomerization unit
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