Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 9.5

UOP PAR-ISOM PROCESS

Nelson A. Cusher
UOP LLC Des Plaines, Illinois

Light straight-run (LSR) naphtha fractions are predominantly C5s and C6s. Some C7s are also present. They are highly paraffinic and have clear research octane numbers (RONC) usually in the 60s. This fraction, which constitutes 10 percent of a typical gasoline pool in the United States, is usually upgraded with paraffin isomerization technology. The use of paraffin isomerization technology 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 and benzene. This technology continues to be important in view of current U.S. and European legislation on reformulated gasoline. The most cost-effective means to upgrade an LSR feedstock in a grassroots situation is the UOP* Penex* process. This process relies on a highly active chlorided alumina catalyst to produce an isomerate product with a RONC of 82 to 85. However, the catalyst is sensitive to contaminants and is not regenerable. Alternatively, refiners with idle processing equipment such as old catalytic reformers or hydrodesulfurization units can consider converting this equipment to the UOP OnceThrough (O-T) Zeolitic Isomerization process (formerly known as the Shell Hysomer process). These conversions can be accomplished quickly and at low cost to provide a 10 to 12 octane number increase for the light naphtha. Zeolitic catalysts are tolerant of contaminants and are regenerable, but operate at relatively high temperatures that limit the maximum octane that can be achieved. With the commercialization of the UOP Par-Isom process, the refiner has another option for light paraffin isomerization. The key to this new process is the LPI-100 catalyst, an innovative, high-performance sulfated metal oxide catalyst with activity approaching that of chlorided alumina catalysts, but with the benefit of being both robust and regenerable. The basic formulation for LPI-100 catalyst was originally developed by Cosmo Research Institute and Mitsubishi Heavy Industries in Japan. With the UOP Par-Isom process, an LSR feedstock can be upgraded to 79 to 82 RONC.

*UOP, Penex, Par-Isom, LPI-100, and HS-10 are service marks and/or trademarks of UOP. Hysomer is a service mark and/or trademark of Shell Oil.

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UOP PAR-ISOM PROCESS 9.42

ISOMERIZATION

PROCESS DISCUSSION
The UOP Par-Isom process is specifically designed for the catalytic isomerization of pentanes, hexanes, and mixtures thereof. The reactions take place in the presence of hydrogen, over a fixed bed of catalyst, and at operating conditions that promote isomerization and minimize hydrocracking. The unit operates at moderate temperature and pressure. Ideally, an isomerization catalyst would convert all the feed paraffins to the highoctane-number branched structures: nC5 to isopentane and nC6 to 2,2- and 2,3-dimethylbutane. These reactions are controlled by a thermodynamic equilibrium that is more favorable at low temperature. The Penex process operates at a lower temperature than the Par-Isom process, which in turn operates at a lower temperature than the Once-Through Zeolitic Isomerization process. Consequently, the Penex process produces the highest product octane, followed by the Par-Isom process, with the Once-Through Zeolitic Isomerization process offering the lowest product octane. Table 9.5.1 shows typical charge and product compositions for a C5-C6 Par-Isom unit. With C5 paraffins, interconversion of normal pentane and isopentane occurs. The C6 paraffin isomerization is somewhat more complex. Since the formation of 2- and 3-methylpen-

TABLE 9.5.1 Typical Estimated Performance, Par-Isom Isomerization Unit 10,000 BPD Hydrogen consumption Light-gas yield C1 C2 C3 Component Flow rate, BPD IC4 NC4 IC5 NC5 Cyclo-C5 2,2-Dimethylbutane 2,3-Dimethylbutane 2-Methylpentane 3-Methylpentante NC6 Methylcyclopentane Cyclo-C6 Benzene C7 Total C4 properties: Specific gravity Reid vapor pressure, kg/cm2 (lb/in2 absolute) Octane number RONC, clear RONC 3 cm3 tetraethyl lead/U.S. gal MONC, clear MONC 3 cm3 tetraethyl lead/U.S. gal 1,602,000 SCF/day 137,000 SCF/day 67,000 SCF/day 246,000 SCF/day Fresh feed to reactor 10 58 1,684 2,907 169 51 193 1,208 880 1,935 195 341 175 194 10,000 0.659 0.8 (10.8) 68.1 88.4 66.4 87.3 Product 278 135 3,185 1,368 169 984 461 1,555 903 572 216 121 0 86 10,033 0.647 1.0 (14.6) 81.8 97.1 79.9 97.8

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UOP PAR-ISOM PROCESS

UOP PAR-ISOM PROCESS

9.43

tane and 2,3-dimethylbutane is limited by equilibrium, the net reaction involves mainly the conversion of normal hexane to 2,2-dimethylbutane. All the feed benzene is hydrogenerated to cyclohexane, and a thermodynamic equilibrium is established between methylcyclopentane and cyclohexane. The octane rating shows an increase of some 13.7 numbers.

PROCESS FLOW SCHEME

The Par-Isom process flow scheme is shown in Fig. 9.5.1 and is identical to the O-T Zeolitic Isomerization process flow scheme. In fact, since the two processes operate over the same pressure range, LPI-100 catalyst is a drop-in replacement for HS-10 catalyst that results in a 2 to 3 octane number improvement. The light naphtha feed is combined with makeup and recycle hydrogen before being directed to the charge heater where the reactants are heated to reaction temperature. A fired heater is not required in the Par-Isom process, due to the much lower reaction temperature needed for LPI-100 catalyst than for zeolitic catalysts. Hot oil or high-pressure steam can be used as the heat source in this exchanger. The heated combined feed is then sent to the isomerization reactor. The reactor effluent is cooled and then sent to a product separator where the recycle hydrogen is separated from the other products. Recovered recycle hydrogen is directed to the recycle compressor and then returned to the reaction section. The liquid product is sent to a stabilizer column where the light ends and dissolved hydrogen are removed. The stabilized isomerate product can be sent directly to gasoline blending. Alternatively, the stabilizer bottoms can be fractionated in a deisohexanizer column to concentrate the normal hexane and low-octane methylpentanes into a sidecut stream. This sidecut stream combines with the fresh feed before entering the Par-Isom reactor. The deisohexanizer column overhead, which is primarily isopentane, 2,2-dimethylbutane, and 2,3-dimethylbutane, is recovered for gasoline blending. A small bottoms drag stream, consisting of C6 naphthenes and C7s, is also removed from the deisohexanizer column and used for gasoline blending or as reformer feed. Product octanes in the range of 85 to 87 RONC can be achieved with this flow scheme.

Makeup gas Stabilizer

Off Gas

Product Separator Rx

Reactor Feed
FIGURE 9.5.1 Par-Isom process flow scheme.

Stabilizer Bottoms

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UOP PAR-ISOM PROCESS 9.44

ISOMERIZATION

CATALYST INFORMATION
Sulfated metal oxide catalysts can be considered to be solid superacids and exhibit high activity for paraffin isomerization reactions. Sulfated metal oxide catalysts form the basis of the new generation of isomerization catalysts that have been actively discussed in the scientific literature in recent years. These catalysts are most commonly tin oxide (SnO2), zirconium oxide (ZrO2), titanium oxide (TiO2), or ferric oxide (Fe2O3) that have been sulfated by the addition of sulfuric acid or ammonium sulfate. Sulfated alumina is not an active catalyst for hydrocarbon reactions. Sulfated metal oxide catalysts have now been commercialized with the introduction of UOPs LPI-100 catalyst. Activity of this new catalyst is considerably higher than that of traditional zeolitic catalysts, equivalent to about 85C (150F) lower reaction temperature. The lower reaction temperature allows for significantly higher product octane, about 82 RONC for a typical feed or 3 numbers higher than a zeolitic catalyst. LPI-100 catalyst is robust and is not permanently deactivated by water or oxygenates in the feedstock. It is also fully regenerable by using a simple oxidation procedure that is comparable to that practiced for zeolitic catalysts. The high activity of the sulfated metal oxide catalyst makes it an ideal candidate for (1) revamping existing zeolitic isomerization units for higher capacity, (2) revamping idle hydrotreaters and reformers for isomerization service, or (3) new units where the full performance advantage of chlorided alumina catalysts is not required or where catalyst stability due to feedstock contaminants is a concern.

COMMERCIAL INFORMATION
As of 2002, eight Par-Isom units have been commissioned that process between 900 and 7500 BPD of feed. Three additional units are in the design/construction phase. Table 9.5.2 provides a summary of Par-Isom investment costs and utility requirements. Information is provided for a grassroots unit. Note that no new major equipment is required when an O-T Zeolitic Isomerization unit is converted to an O-T Par-Isom unit of the same feed capacity.

WASTES AND EMISSIONS

No wastes or emissions are created by the Par-Isom* process. Product stabilization, however, does result in small amounts of liquefied petroleum gas (LPG) (C3 C4, rich in IC4) and stabilizer overhead (H2 C1 C2) products. The stabilizer overhead products are usually used as fuel. The LPG is a valuable by-product that is blended elsewhere in the refinery.

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TABLE 9.5.2

O-T Par-Isom Process Economics and Performance 870 0.07 61 (240) 0.16 (0.03) 0.46 (1.00) 0.55 (1.21) 2.76.1 (49) 7982 9798 510

Economics New unit cost, $/BPSD Utilities, per BPSD feed Electric power (new unit only), kW Fuel consumed (conversion only @ 90% efficiency), kcal/h (Btu/h) Water 17C rise, m3/day (gal/min) MP steam, kg/h (lb/h) LP steam, kg/h (lb/h) Hydrogen consumption, m3/day (SCF/h) Typical performance Isomerate research octane number, clear C5 isomerate yield, LV % Catalyst expected life, years Basis: Battery limits; U.S. Gulf Coast, 2002; 10,000 BPSD feed, including stabilizer

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UOP PAR-ISOM PROCESS

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