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CHAPTER 9.4
UOP TIP AND
ONCE-THROUGH ZEOLITIC
ISOMERIZATION PROCESSES
Nelson A. Cusher
UOP LLC
Des Plaines, Illinois
INTRODUCTION
Light straight-run (LSR) naphtha fractions made in the refinery are predominantly C5’s
and C6’s. Some C7’s are also present. They are highly paraffinic and have clear research
octane numbers (RONC) usually in the 60s. The nonnormal components have higher
octanes than normal paraffins (Table 9.4.1) and are excellent gasoline-blending feedstocks.
For the refiner who wants to upgrade the octane of a gasoline pool and has use for a high-
purity normal paraffin product, UOP*’s IsoSiv* separation technology is a good fit.
However, if octane improvement is of primary importance, isomerization technology is the
best choice.
Paraffin isomerization to upgrade the octane of light-naphtha streams has been known
to the refining industry for many years and has gained importance since the onset of the
worldwide reduction in the use of lead antiknock compounds. This technology continues
to be important in view of current U.S. legislation on reformulated gasoline.
The most cost-effective means to upgrade an LSR feedstock in a grassroots situation is
UOP’s Penex* process, which is discussed further in Chap. 9.3. However, refiners with
idle hydroprocessing equipment, such as old catalytic reformers or hydrodesulfurization
units, can consider converting this equipment to a UOP Once-Through (O-T) Zeolitic
Isomerization process (formerly known as the Shell Hysomer† process). The process
scheme is similar to that of a simple hydrotreater, as shown in Fig. 9.4.1, and conversions
can be accomplished quickly and at low cost. With O-T Zeolitic Isomerization, a 10 to 12
octane-number increase for the C5–71°C (160°F) light naphtha can be achieved.
For those refiners who need more octane than can be achieved from the once-through
operation, an additional 8 to 10 RONC can be gained by adding molecular sieve adsorp-
tion to the O-T Zeolitic Isomerization process. Molecular sieve adsorption is used to
extract the unreacted normal paraffins so they can be recycled to extinction. This approach
9.29
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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES
9.30 ISOMERIZATION
Process Chemistry
Process Description
The O-T Zeolitic Isomerization process is a fixed-bed, vapor-phase process for the cat-
alytic isomerization of low-octane normal pentane or normal hexane or both to high-octane
isoparaffins. The isomerization reaction is carried out at 245 to 270°C (470 to 520°F) and
21 to 35 kg/cm2 (300 to 500 lb/in2 gage) in the presence of hydrogen. Equipment require-
ments are a reactor vessel, heater, recycle hydrogen compressor, feed-product heat
exchanger, product cooler, phase separator drum, and product stabilizer section.
9.32 ISOMERIZATION
Reactors. With catalytic reformers that were originally designed for a weight hourly
space velocity (WHSV) comparable to that of the O-T Zeolitic Isomerization process,
no major modifications to the reactors are required except to eliminate interstage
Note: WHSV ⫽ weight hourly space velocity; HC ⫽ hydrocarbon; SCFB ⫽ standard cubic feet per barrel.
heating. Because of the difference in feed densities, the O-T Zeolitic Isomerization
catalyst requirement is typically about 20 percent less than the reformer catalyst
requirement.
If the O-T Zeolitic Isomerization unit is to be designed for a lower WHSV or if recy-
cle of normal paraffins to obtain the maximum octane increase is desired, converting from
internal to external insulation can achieve about a 25 to 30 percent increase in reactor vol-
ume. This increase is possible because of the relatively low operating temperature for the
O-T Zeolitic Isomerization process; however, the material used to construct the reactor
shell should be checked for pressure or temperature limitations.
9.34 ISOMERIZATION
Heaters and Heat Exchangers. Heat exchange equipment and heaters are usually
more than adequate. Interstage reheaters between reactors are not required because the
isomerization reaction is mildly exothermic.
Feed Pump. Because of differences in feed gravity, feed rate, vapor pressure, and
possible net positive suction head (NPSH), a new feed pump may be required.
Stabilizer System. In the O-T Zeolitic Isomerization process, the amount of light
ends produced is substantially less than in the reforming process. In any case, where a
reformer has been converted to an O-T Zeolitic Isomerization unit, the stabilizer feed
rate is higher even though the stabilizer overhead product is lower than in the
reforming operation. The small amount of light ends plus a bottoms product with a
higher vapor pressure may dictate an increased reflux rate or a column retray or both.
Commercial Information
The need for a high-octane product to replace the octane lost with lead phaseout and ben-
zene reduction in the gasoline pool has placed more emphasis on isomerization. As previ-
ously noted, the attractiveness of the O-T Zeolitic Isomerization process is that it can be
adapted to an existing idle hydrotreater, catalytic reformer, or other hydroprocessing unit
with minimal investment. The actual time to modify a unit ranges from a few days to a few
weeks.
TABLE 9.4.4 Typical Estimated Performance, O-T Zeolitic Isomerization Unit, 10,000
BPD
Note: BPD ⫽ barrels per day; SCF ⫽ standard cubic feet; RON ⫽ research octane number; MON ⫽
motor octane number; TEL ⫽ tetraethyl lead; i ⫽ iso; n ⫽ normal.
amount is only about half of the cost of a grassroots installation. Expected catalyst life is
10 to 15 years.
TIP PROCESS
General Description
Some refiners need more octane from the LSR naphtha fraction than is possible from the
O-T Zeolitic Isomerization process. As previously noted, the TIP process combines the
O-T Zeolitic Isomerization process with UOP’s naphtha IsoSiv process to yield an 87 to
90 RONC product, an improvement of approximately 20 numbers. The TIP unit can be
built grassroots, or a UOP IsoSiv unit can be added to an existing O-T Zeolitic
Isomerization unit to convert it to a TIP unit. In this type of revamp, generally all existing
equipment can be used.
9.36 ISOMERIZATION
*Basis: Battery limits; U.S. Gulf Coast, 2001, 4000–6000 BPSD, including new stabilizer, new piping
and instrumentation, engineering, and catalyst.
The TIP process uses adsorption technology to remove and recycle the unconverted
normal paraffins. During the adsorption step, a shape-selective molecular sieve removes all
the unconverted normal paraffins from the isomerate to allow the branched-chain isomers
to pass through. These adsorbed normals are then desorbed by stripping with recycle
hydrogen and passed directly into the isomerization reactor. Because the entire process is
carried out in the vapor phase, utility requirements are low. The entire process operates at
a constant low pressure. The presence of hydrogen during the desorption step prevents the
buildup of coke on the adsorbent. Like the catalyst, the adsorbent can be regenerated in situ
if an upset condition causes coking.
the adsorbers rather than at the isomerization reactor. This feed-entry point allows the non-
normal components and isoheptanes to pass into the final isomerate product without first
passing through the isomerization reactor, where some of the heptanes are hydrocracked
to liquefied petroleum gas (LPG). With feedstocks having a low normal-paraffin content,
it is also more efficient to have the fresh feed enter the system just upstream of the adsor-
bers to recover the nonnormal components. Only the adsorbed normal paraffins are then
sent to the resulting smaller isomerization reactor.
Feeds with high levels of benzene can be processed initially in either the reactor sec-
tion or the adsorption section. Benzene is saturated completely to cyclohexane in the
reactor section, thereby producing a benzene-free isomerate product. For feeds with high
levels of benzene, presaturation in a separate reactor at a high space velocity is used to
remove the heat of saturation from the TIP reactor. This technology is known as TIP-
Plus.* Sending the feed to the adsorption section allows the high-octane benzene to pass
into the isomerate product. For feeds that are best processed in the adsorber section first
but need to minimize benzene in the product, the saturation-section effluent can be sent
to the adsorption section of the TIP-Plus process. The refiner needs to evaluate both
octane and benzene target levels to determine the proper feed point.
The TIP unit is normally designed with the capability for an in situ oxidative regener-
ation of the catalyst and the adsorbent to minimize downtime in the event of an unexpect-
ed upset that might coke the catalyst or the adsorbent.
Commercial Information
As of early 2002, more than 30 TIP units were in operation worldwide. Tables 9.4.6 and
9.4.7 provide a summary of typical TIP process yields, product properties, capital costs,
utility requirements, and overall operating costs. A 0.6 power factor applied to the ratio of
fresh-feed rates can be used with the cost given in Table 9.4.7 for a quick estimate of the
9.38 ISOMERIZATION
TABLE 9.4.6 Typical Estimated Yields for the TIP Process, 10,000 BPD
investment costs for different-size TIP units. Utilities and catalyst-adsorbent requirements
tend to increase in direct proportion to an increase in fresh feed rate.
No wastes or emissions are created by the O-T Zeolitic Isomerization or TIP processes.
Product stabilization, however, does result in small amounts of LPG (C3 + C4, rich in iC4)
and in stabilizer vent (H2 + C1 + C2) products. The stabilizer vent products are usually used
as fuel. The LPG is a valuable by-product that is blended elsewhere in the refinery.
Economics:
Investment,* $/BPSD 3200–4000
Catalyst and adsorbent inventory, $/BPSD 240
Utilities:
Fuel consumed (90% furnace efficiency), million kcal/h (million Btu/h) 7.8 (31)
Water at 17°C rise (31°F), m3/day (gal/min) 2159 (396)
Power, kWh 1455
Steam at 10.5 kg/cm2 (150 lb/in2 gage) kg/h (lb/h) 2.8 (6.2)
Hydrogen consumption (70% hydrogen purity), 1000 m3/day (1000 SCF/h) 17.7 (26)
*Battery limits, U.S. Gulf Coast, 2001, feed rate 4000–6000 BPSD.