Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 10.5

UOP ISOSIV PROCESS

Nelson A. Cusher
UOP LLC Des Plaines, Illinois

INTRODUCTION
Light straight-run (LSR) naphtha fractions made in the refinery are predominantly C5s through C7s, with traces of C8s. They are highly paraffinic and contain moderate amounts of naphthenes, low aromatics, and no olefins. The average clear research octane number (RONC) is usually in the 60s. The paraffinicity of light naphtha is what makes it a desirable petrochemical cracking stock. The aromatic rings are too thermally stable for cracking, and the naphthenes produce more liquid products. The straight-chain normal paraffins produce more ethylene and less pyrolysis gasoline than the branched-chain paraffins. Figure 10.5.1 compares pyrolysis unit yields from a normal paraffin feed with yields from a mixed natural gasoline feed. The yields are based on a single-pass pyrolysis operation at equivalent high furnace severities for both feeds. The normal paraffin feed was extracted from a C5 through C9 natural gasoline stream. The natural gasoline feed contained 54.4 percent straight-chain paraffins and 45.6 percent branched and cyclic hydrocarbons. The ethylene yield is about 30 percent higher for the all-normals fractions. Propylene, butene, and light-gas yields decrease slightly. The pyrolysis gasoline yield is considerably reduced. As the endpoint of naphtha is decreased, the paraffinicity of the stream increases; as a result, ethylene production increases and the production of pyrolysis gasoline and fuel oil decreases. The LSR naphthaespecially the 70C (C5160F) portion, which is about 95 percent paraffinicis therefore a prime substitute for natural gas liquids as an ethylene plant feed. The nonnormal components of the LSR naphtha fraction have higher octanes than the normal paraffins (Table 10.5.1) and are excellent gasoline blending components. UOP*s IsoSiv* process uses molecular sieves to physically remove normal paraffins from the LSR feedstock. In the past, gasoline-range IsoSiv units were primarily used to produce specialty chemicals. The normal paraffin product having a 95 to 98 percent purity was cut into single-carbon-number fractions for special solvents. The normalparaffinfree fraction was usually sent to the gasoline pool as an octane booster. The more recent IsoSiv units were built to produce high-octane gasoline components; the normal paraffin by-product was sold as petrochemical feedstock or sent to an isomerization reactor.
*Trademark and/or service mark of UOP.

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UOP ISOSIV PROCESS 10.64

SEPARATION PROCESSES

FIGURE 10.5.1

Pyrolysis yield data.

TABLE 10.5.1 Component

Properties of Common Gasoline Components Molecular weight 58.1 58.1 72.1 72.1 72.1 70.0 86.2 86.2 86.2 86.2 86.2 84.2 100.2 78.1 100.2 84.2 100.2 100.2 100.2 100.2 100.2 92.1 106.2 120.2 120.2 142.3 Boiling point, C (F) 11.7 (10.9) 0.5 (31.1) 9.4 (49.0) 27.9 (82.2) 36.1 (96.9) 49.3 (120.7) 49.7 (121.5) 58.0 (136.4) 60.3 (140.5) 66.3 (145.9) 68.7 (155.7) 71.8 (161.3) 79.2 (174.6) 80.1 (176.2) 80.5 (176.9) 80.7 (177.3) 80.9 (177.6) 86.1 (186.9) 89.8 (193.6) 90.1 (194.1) 91.9 (197.5) 110.6 (231.1) 136.2 (277.1) 152.4 (306.3) 165.1 (329.2) 174.0 (345.2) Density, kg/m3 (lb/gal) 562 (4.69) 582 (4.86) 596 (4.97) 623 (5.20) 629 (5.25) 749 (6.25) 664 (5.54) 664 (5.54) 667 (5.57) 652 (5.44) 657 (5.48) 753 (6.28) 676 (5.64) 882 (7.36) 676 (5.64) 782 (6.53) 693 (5.78) 696 (5.81) 699 (5.83) 681 (5.68) 690 (5.76) 870 (7.26) 870 (7.26) 864 (7.21) 881 (7.35) 732 (6.11) RONC 100+ 93.6 116 92.3 61.7 100 91.8 101.7 73.4 74.5 24.8 91.3 92.8 100+ 83.1 83 112 98 88.5 55 65 100+ 100+ 100+ 100+ 53

Isobutane n-butane Neopentane Isopentane n-pentane Cyclopentane 2,2-dimethlybutane 2,3-dimethylbutane 2-methylpentane 3-methylpentane n-hexane Methylcyclopentane 2,2-dimethylpentane Benzene 2,4-dimethylpentane Cyclohexane 2,2,3-trimethylbutane 3,3-dimethylpentane 2,3-dimethylpentane 2,4-dimethylpentane 3-methylhexane Toluene Ethylbenzene Cumene 1-methyl-2-ethylbenzene n-decane

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UOP ISOSIV PROCESS

UOP ISOSIV PROCESS

10.65

GENERAL PROCESS DESCRIPTION

The LSR naphtha fractions usually contain 40 to 50 percent normal paraffins. The IsoSiv process (Fig. 10.5.2) separates the normal paraffins from a hydrocarbon mixture by selective adsorption on a molecular sieve material. This material is a crystalline zeolite having uniform pore dimensions of the same order of magnitude as the size of individual hydrocarbon molecules. The molecular sieve used for normal paraffin separation has pore openings in the crystalline structure that are sized to allow molecules of normal paraffin to pass through the pore openings into the internal crystal cavity, where they are retained. Nonnormal hydrocarbons, such as isoparaffins, naphthenes, and aromatics, have larger molecular diameters and are, therefore, excluded from entering the crystal cavity through the pore opening. The heart of the IsoSiv process is the adsorber section, which consists of vessels filled with molecular sieve adsorbent. The LSR feedstock is fed into one end of an adsorber vessel. The normal paraffins in the feedstock remain in the vessel by being adsorbed into the molecular sieve, and the remainder of the feedstock passes out the other end of the vessel as a nonnormal product. In a subsequent process step, the normal paraffins are recovered from the adsorber vessel as a separate product by use of a purge material. All process hardware in an IsoSiv unit is conventional refinery equipment, such as pumps, furnaces, heat exchangers, and compressors, that is designed to deliver the feedstock and the purge material to the adsorber section. Typical performance (Table 10.5.2) results in an isomer product that is 98 to 99 percent free of normal paraffins and a normal paraffin product of 95 to 98 percent purity. The highoctane isomer product can have a RON approximately 15 numbers higher than the feed, depending on feed composition. The IsoSiv-grade molecular sieve adsorbent is fully regenerable and has an expected life of 10 to 15 years.

FIGURE 10.5.2

UOP IsoSiv process.

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UOP ISOSIV PROCESS 10.66 TABLE 10.5.2

SEPARATION PROCESSES

Typical Performance 9899% 15 higher than feed RONC 9598% 1015 years

Isomer product purity Isomer research octane Normal-paraffin product purity Adsorbent expected life

PROCESS PERSPECTIVE
The UOP IsoSiv process gained early acceptance and has maintained a leading position to the present day. The technology of normal paraffin separation by adsorption had its start in the late 1950s in the separation of normal paraffins from gasoline for octane improvement purposes. The first commercial application was an IsoSiv unit installed by the South Hampton Company of Silsbee, Texas. Today more than 45 IsoSiv units are operating as stand-alone units or as part of UOPs TIP* technology in the United States, Australia, Europe, Asia, and South America. These units range in size from 1000 to 35,000 barrels per stream day (BPSD) of feed capacity.

DETAILED PROCESS DESCRIPTION

The naphtha-range IsoSiv process makes use of the highly selective adsorption capability of a molecular sieve. The process is run at a constant, elevated temperature and pressure. Vapor-phase operation is used to provide straightforward processing. Continuous processing is accomplished through cyclic operation that uses valves actuated by standard, fully automatic sequencing controls to switch adsorption beds. A steady flow of feed and products and constant product purity are maintained. All operating conditions are within the temperature and pressure ranges common to refinery and petrochemical operation. The basic IsoSiv cycle consists of an adsorption and a desorption step. Adsorption The feed stream is pumped through the heat exchanger, where it is heated by the nonnormal product, and then passes through a feed heater to an adsorption bed. It is then passed upward through one adsorber vessel, where the normal paraffins are selectively adsorbed in the bed. As the normal paraffins are adsorbed, the liberated heat of adsorption creates a temperature front that travels through the bed. This front closely coincides with the mass-transfer front and gives an indication of when the adsorption step should be terminated to prevent the normal paraffins from breaking through the effluent end of the bed. This temperature front is used in the field to set the cycle timer to prevent the front from reaching the bed exit. The unadsorbed isomers and cyclic hydrocarbons that pass through the beds are heat-exchanged against the feed stream to recover heat. This stream is then cooled and condensed, and the high-octane liquid is taken as product. The uncondensed vapors are reused as part of the nonadsorbable purge. Desorption After the adsorption step, the beds are countercurrently purged with a nonadsorbable medium. This countercurrent purging desorbs the normal paraffins and sweeps these desorbed
*Trademark and/or service mark of UOP.

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UOP ISOSIV PROCESS

UOP ISOSIV PROCESS

10.67

vapors from the bed, thus maintaining the average partial pressure of the desorbate below the value in equilibrium with the loading on the bed. The continuous removal of the desorbate vapor and the simultaneous transfer of the absorbed phase to the purge gas in an attempt to establish equilibrium drive the desorption stage to completion. A complete removal of the normal paraffin adsorbate is not achieved on each desorption. An economic balance between the bed size, as determined by the fraction of normal adsorbate removed (delta loading), and the purge required determines the degree of normals removed. This stream is then cooled and condensed, and the liquid is taken as normal product. The uncondensed vapors are reused as part of the purge medium. The elevated temperatures used for vapor-phase adsorption can cause a gradual formation of coke on the beds. To remove any accumulation, a burn-off procedure is incorporated to reactivate the adsorbent at required times. This burn-off capability provides a built-in safeguard against permanent loss of bed capacity as a result of operating upsets. An in situ regeneration procedure is used to burn off the coke deposits and restore full adsorbent capacity.

PRODUCT AND BY-PRODUCT SPECIFICATIONS

The normal product purity is typically 95 to 98 percent. The purity of the isomer product is typically 98 to 99 percent. The high-octane isomer product can have a RON approximately 15 numbers higher than the feed, depending on feed composition.

WASTE AND EMISSIONS

No waste streams or emissions are created by the IsoSiv process. Isomer and normal products are usually stabilized, however. The result is a liquefied petroleum gas product (C3 + C4, rich in isobutane) and a stabilizer vent (H2 + C1 + C2).

PROCESS ECONOMICS
Many factors influence the cost of separating isoparaffins and normal paraffins. These factors include feedstock composition, product purity, and the capacity and location of the unit. Location affects costs of labor, utilities, storage, and transportation. With this in mind, Table 10.5.3 presents investment and utility requirements. In summary, commercially proven large-scale production technology is available today for the economic production of high-quality isoparaffins and normal paraffins.

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UOP ISOSIV PROCESS 10.68

TABLE 10.5.3
SEPARATION PROCESSES

UOP IsoSiv Process Economics and Performance* 21002800 205 0.0006 (0.0022) 0.82 (0.15) 0.40 0.75 (1.1)

Investment, $/BPSD of normal paraffins in feed: Erected capital cost Adsorbent inventory Utilities, per BPSD: Fuel consumed at 90% efficiency, million kcal/h (million Btu/h) per BPSD of total feed Water at 17C (31F) rise, m3/day BPSD (gal/min) per BPSD of normal paraffins in feed Power, kWh per BPSD of normal paraffins in feed Hydrogen makeup at 70% H2 purity (solution loss), m3/day (SCF/h) per BPSD of total feed

*Basis: Battery-limits Gulf Coast location, 2001, excluding product stabilization. Normal-paraffin feed rates of 3000 to 8000 BPSD. Note: SCF standard cubic feet.

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