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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

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

*Trademark and/or service mark of UOP.


†Trademark and/or service work of Shell Oil.

9.29
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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

9.30 ISOMERIZATION

TABLE 9.4.1 Properties of Common Gasoline Components

Molecular Boiling Density,


weight point,* °F * lb/gal RONC
Isobutane 58.1 10.9 4.69 100+
n-butane 58.1 31.1 4.86 93.6
Neopentane 72.1 49.0 4.97 116
Isopentane 72.1 82.2 5.20 92.3
n-pentane 72.1 96.9 5.25 61.7
Cyclopentane 70.0 120.7 6.25 100
2,2-dimethylbutane 86.2 121.5 5.54 91.8
2,3-dimethylbutane 86.2 136.4 5.54 101.7
2-methylpentane 86.2 140.5 5.57 73.4
3-methylpentane 86.2 145.9 5.44 74.5
n-hexane 86.2 155.7 5.48 94.8
Methylcyclopentane 84.2 161.3 6.28 91.3
2,2-dimethylpentane 100.2 174.6 5.64 92.8
Benzene 78.1 176.2 7.36 100+
2,4-dimethylpentane 100.2 176.9 5.64 83.1
Cyclohexane 84.2 177.3 6.53 83
2,2,3-trimethylbutane 100.2 177.6 5.78 112
3,3-dimethylpentane 100.2 186.9 5.81 98
2,3-dimethylpentane 100.2 193.6 5.83 88.5
2,4-dimethylpentane 100.2 194.1 5.68 55
3-methylhexane 100.2 197.5 5.76 65
Toluene 92.1 231.1 7.26 100+
Ethylbenzene 106.2 277.1 7.26 100+
Cumene 120.2 306.3 7.21 100+
1-methyl-2-ethylbenzene 120.2 329.2 7.35 100+
n-decane 142.3 345.2 6.11 ⫺53

*The values for °C and kg/m3 can be found in Table 10.5.1.

FIGURE 9.4.1 UOP Once-Through Zeolitic Isomerization process.

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

UOP TIP AND O-T ZEOLITIC ISOMERIZATION PROCESSES 9.31

of complete isomerization is referred to as UOP’s TIP* process. Because O-T Zeolitic


Isomerization is an integral part of the TIP process, the ensuing discussion begins with the
once-through operation and concludes with a discussion of TIP.

O-T ZEOLITIC ISOMERIZATION PROCESS

Process Chemistry

Thermodynamically, low temperatures are preferred for obtaining maximum amounts of


branched paraffins in the reaction product. Operation below 150°C (302°F) for maximum
activity requires a catalyst that uses a halide activator. For these catalysts, feed drying is
required to eliminate any corrosion or catalyst stability concerns.
The catalyst used in the O-T Zeolitic Isomerization process, however, is based on a
strongly acidic zeolite with a recoverable noble-metal component. No external acid acti-
vators are used and the catalyst does not produce a corrosive environment. Therefore, feed
drying is not necessary.
The catalyst base behaves as an acid of the Brönsted type because it has a high activi-
ty for normal-pentane isomerization in the absence of a metal component. At a relatively
low hydrogen partial pressure, the carbonium ion concentration generated by the activated
low-sodium zeolite is apparently higher than it would have been if the paraffin-olefin equi-
librium had been established. This excessive carbonium ion concentration leads to not only
high initial conversion but also unstable operation and low selectivity under preferred
operating conditions (Fig. 9.4.2). This figure also shows that incorporation of the metal
function stabilizes the conversion and lowers the initial activity. These results are to be
ascribed to the lower olefin and carbonium ion concentration in the presence of the dual-
function catalyst as a result of the paraffin-olefin equilibrium.
The reaction mechanism on the new catalyst is shown in Fig. 9.4.3. Carbonium ions
and isoparaffins are generated from normal paraffins by a combination of hydride-ion
abstraction and hydride-ion transfer reactions. In the adsorbed state, skeletal rearrange-
ment reactions occur. This reaction is the horizontal path shown in Fig. 9.4.3.
Alternatively, while the normal pentane is in the carbonium ion state (nP+ or iP+), it may
surrender a proton to form an olefin, which in turn is hydrogenated to form a paraffin
(these two paths are vertical).
Even a minute amount of the noble metal stabilizes the conversion to isopentane,
provided that the noble metal is well dispersed and distributed throughout the zeolite
(Table 9.4.2). However, in commercial applications, more than the minimum amount of
noble metal is required. Normally the catalyst contains a few tenths of a percent of pre-
cious metal. Proper catalyst preparation methods and start-up procedures are essential
for optimal results.

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.

*Trademark and/or service mark of UOP.

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

9.32 ISOMERIZATION

FIGURE 9.4.2 Effect of noble-metal addition


on n-pentane isomerization. (Selectivity for
isopentane overcracking is indicated in parenthe-
ses.)

FIGURE 9.4.3 Isomerization reaction path.

A comparison of catalytic reforming and O-T Zeolitic Isomerization appears in Table


9.4.3. A brief discussion about the required equipment from the perspective of converting
an existing hydrotreater follows.

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

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UOP TIP AND O-T ZEOLITIC ISOMERIZATION PROCESSES 9.33

TABLE 9.4.2 Influence of Metal Load on Zeolite on


Hydroisomerization of n-Pentane.

mol metal/100 g zeolite First-order rate constant


0.000 0.12
0.025 1.5
0.25 1.6
2.00 2.0
5.4 2.3

TABLE 9.4.3 Comparison of Catalytic Reforming and O-T Zeolitic Isomerization

Catalytic O-T Zeolitic


reforming Isomerization
Feed composition C7+ C5-C6
Feed gravity, °API 52–62 88–90
Operating pressure, kg/cm2 (lb/in2 gage) 14–35 (200–500) 21–35 (300–500)
Operating temperature, °C (°F) About 510 (950) About 260 (500)
Feed, WHSV 1–5 1–3
H2/HC ratio, mol/mol 5–10 1–4
H2, SCFB 500–1700 produced About 70 required
Heat of reaction Highly endothermic Nearly isothermal
Reid vapor pressure, kg/cm2 (lb/in2 gage)
Feed 0.05–0.07 (0.7–1.0) 0.8–1.0 (12–14)
Product 0.2–0.4 (3–6) 0.9–1.1 (13–16)
Catalyst regeneration Continuous to about Every 2 to 3 years
1 year periodic

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.

Compressors. The recycle-compressor capacity for a reformer is usually more than


adequate for the O-T Zeolitic Isomerization process. A 25 kg/cm2 (350 lb/in2 gage)
reformer will have about twice the capacity required for the O-T Zeolitic
Isomerization process. In plants containing two compressors, each with a 50 percent
capacity, one compressor can be shut down.
Makeup hydrogen for the O-T Zeolitic Isomerization process can be reformer net gas.
If the reformer supplying the hydrogen is a low-pressure unit, a small makeup compressor
is required. For a O-T Zeolitic Isomerization unit processing 5000 barrels per day (BPD)
of feed, hydrogen makeup is typically about 500,000 standard cubic feet per day
(SCF/day).

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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.

Commercial Installations. As of early 2002, more than 30 O-T Zeolitic


Isomerization units have been commissioned to process 1000 to 13,500 BPD of feed.
About half of these are catalytic-reformer or hydrotreater conversions. One unit was
assembled from assorted surplus refinery equipment. Of the conversions, one unit is
arranged so that it can be operated as either a reformer or a O-T Zeolitic Isomerization
unit by switching a few spool pieces.
The oldest of the converted units started up in 1970 in La Spezia, Italy. This unit was
integrated with a catalytic reformer so that both units have a common recycle-gas com-
pressor system, product-cooling train, and stabilizer section. Combinations of this sort
often result in capital savings of 20 to 40 percent compared to stand-alone isomerization
and reforming units. In 10 years of operation, the catalyst in the La Spezia unit was regen-
erated in situ four times. Typical cycle lengths for O-T Zeolitic Isomerization units are 3
to 4 years.

Typical Performance. Paraffin isomerization is limited by thermodynamic


equilibrium so that a once-through, or single-pass, isomerization reactor provides only
partial conversion of the normal paraffins. In the reactor, C 5 -C 6 paraffins are
isomerized to a near-equilibrium mixture, and aromatics become saturated to
naphthenes, which, in turn, are partially converted into paraffins. Olefins in the feed
are saturated, and C7+ paraffins are mostly hydrocracked to C3 to C6 paraffins.
Tables 9.4.4 and 9.4.5 provide a summary of typical O-T Zeolitic Isomerization yields,
product properties, conversion costs, utility requirements, and overall operating costs.
Typical C5+ isomerate yield is 97 to 98 liquid volume percent (LV %) on feed and the
octane number is increased by about 10 to 12, resulting in an isomerate quality of 77 to 80
RONC.
Usually no new major equipment is required when a reformer is converted to an O-T
Zeolitic Isomerization unit of the same feed capacity. Thus, the only costs are for new pip-
ing and instrumentation, engineering, and a charge of O-T Zeolitic Isomerization catalyst.
For a unit with a feed rate of 5000 BPD, capital costs will total $3.0 to $4.5 million. This

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

UOP TIP AND O-T ZEOLITIC ISOMERIZATION PROCESSES 9.35

TABLE 9.4.4 Typical Estimated Performance, O-T Zeolitic Isomerization Unit, 10,000
BPD

Component Fresh feed to reactor Product


3
Hydrogen consumption, m /h (1000 SCF/day) 2018 (1710) —
Light gas yield, m3/h (1000 SCF/day):
C1 — 333 (283)
C2 — 180 (152)
C3 — 292 (248)
C4 + streams, LV % on feed:
iC4 0.10 2.50
nC4 0.58 1.41
iC5 16.84 30.39
nC5 29.07 16.17
Cyclo-C5 1.69 1.24
2,2-dimethylbutane 0.51 8.26
2,3-dimethylbutane 1.93 3.74
2-methylpentane 12.08 14.43
3-methylpentane 8.80 9.21
nC6 19.35 8.24
Methylcyclopentane 1.95 3.35
Cyclo-C6 3.41 0.96
Benzene 1.75 0.0
C7 1.94 0.97
Total 100.00 100.87
C4+ properties:
Specific gravity 0.659 0.648
Reid vapor pressure, kg/cm3 (lb/in2) 0.8 (10.8) 1.0 (14.2)
Octane number:
RON, clear 68.1 79.5
RON + 3 cm3 TEL/U.S. gal 88.4 95.5
MON, clear 66.4 77.6
MON + 3 cm3 TEL/U.S. gal 87.3 96.3

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.

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

9.36 ISOMERIZATION

TABLE 9.4.5 O-T Zeolitic Isomerization Conversion Economics and Performance*

Total capital required, $/BPSD 750


Utilities, per BPSD feed:
Fuel consumed (90% efficiency), million kcal/h (million Btu/h) 0.0006 (0.0025)
Water at 17°C rise, m3/day (gal/min) 0.33 (0.06)
Power, kWh 0.05
Steam at 10.5 kg/cm2 (150 lb/in2 gage), saturated, kg/h (lb/h) 0.5 (1.1)
Hydrogen consumption, m3/day (SCF/h) 2.7–6.1 (4–9)
Typical performance:
Isomerate, RONC 77–80
C5+ isomerate yield, LV % 97–98
Catalyst expected life, years 10–15

*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.

Process Description of TIP

The TIP process is a constant-pressure vapor-phase process operating at a moderate pres-


sure, 14 to 35 kg/cm2 (200 to 500 lb/in2 gage) range, and moderate temperatures, 245 to
370°C (475 to 700°F). Hydrogen at a sufficient partial pressure must be present during iso-
merization to prevent coking and deactivation of the catalyst. A simplified schematic flow
sheet is shown in Fig. 9.4.4.
Hydrotreated fresh feed is mixed with the hot recycle stream of hydrogen and C5-C6
normal paraffins prior to entering the isomerization reactor. A small stream of makeup
hydrogen is also added to the feed of the reactor. The reactor effluent, at near-equilibrium
isomerization composition, is cooled and flashed in a separator drum. The liquid product,
which contains some unconverted low-octane normal paraffins, is vaporized and passed
into a bed of molecular-sieve adsorbent, where the straight-chain normals are adsorbed for
recycle back to the isomerization reactor. The branched-chain isomers and cyclic hydro-
carbons, which have molecular diameters greater than the diameter of pores in the molec-
ular-sieve adsorbent, cannot be adsorbed and exit from the absorbent bed essentially free
of normal paraffins. This isomerate product is stabilized as required to remove any excess
hydrogen, 1 to 2 percent cracked products, and any propane or butane introduced with the
makeup hydrogen. The hydrogen purge gas from the separator is circulated by means of a
recycle compressor through a heater and is then used as a purge gas to strip the normal
paraffins previously adsorbed on the molecular-sieve adsorbent bed. The hydrogen plus
desorbed normals is then mixed with the fresh feed upstream of the isomerization reactor.
The isomerization section and the adsorption section of a TIP unit share a common recy-
cle hydrogen loop.
Feedstocks that contain an appreciable amount of heptanes or nonnormal components
use an alternative feed point (Fig. 9.4.4). The fresh feed enters the system just upstream of

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

UOP TIP AND O-T ZEOLITIC ISOMERIZATION PROCESSES 9.37

FIGURE 9.4.4 TIP flow scheme.

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

*Trademark and/or service mark of UOP.

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UOP TIP AND ONCE-THROUGH ZEOLITIC ISOMERIZATION PROCESSES

9.38 ISOMERIZATION

TABLE 9.4.6 Typical Estimated Yields for the TIP Process, 10,000 BPD

Fresh feed Adsorber Recycle Isomerate


Component to reactor feed paraffins product
H2 consumption, m3/h (1000 SCF/day) 2175 (1844) — — —
Light gas yield, m3/h (1000 SCF/day):
C1 — 190 (161) — —
C2 — 81 (69) — —
C3 — 311 (264) — —
C4+ streams, BPSD:
iC4 10 337 194 288
nC4 58 1,035 1,247 136
iC5 1,684 5,254 1,446 4,523
nC5 2,907 3,188 3,411 142
Cyclo-C5 169 153 33 132
2,2-dimethylbutane 51 1,052 215 910
2,3-dimethylbutane 193 528 98 458
2-methylpentane 1,208 2,042 368 1,771
3-methylpentane 880 1,307 230 1,134
nC6 1,935 1,272 1,301 22
Methylcyclopentane 195 397 68 344
Cyclo-C6 341 113 19 98
Benzene 175 0 0 0
C7 194 103 15 89
Total 10,000 16,781 8,645 10,047
C4+ properties:
Specific gravity 0.659 0.642 0.632 0.640
Reid vapor pressure, kg/cm2 (lb/in2) 0.8 (10.8) 1.2 (16.7) 1.4 (20.6) 1.3 (19.2)
Octane number:
RON, clear 68.1 79.7 70.7 88.3
RON+3 cm3 TEL/U.S. gal 88.4 95.6 90.1 100.9
MON, clear 66.4 77.7 69.4 85.8
MON+3 cm3 TEL/U.S. gal 87.3 96.4 90.4 102.5

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.

Wastes and Emissions

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.

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UOP TIP AND O-T ZEOLITIC ISOMERIZATION PROCESSES 9.39

TABLE 9.4.7 TIP Process: Economics and Performance

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.

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