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    Isomerization: P A R T 9

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    Bharavi K S
    Major source of benzene in most refineries is the catalytic reformer. Reformate typically contributes 50 to 75 percent of the benzene in the gasoline pool. Reformation can be used to produce petrochemical-grade benzane. Isomerization increases the octane of the stream by isomerizing the paraffins.

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    Isomerization: P A R T 9

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    Bharavi K S
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    Major source of benzene in most refineries is the catalytic reformer. Reformate typically contributes 50 to 75 percent of the benzene in the gasoline pool. Reformation can be used to produce petrochemical-grade benzane. Isomerization increases the octane of the stream by isomerizing the paraffins.

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    Major source of benzene in most refineries is the catalytic reformer. Reformate typically contributes 50 to 75 percent of the benzene in the gasoline pool. Reformation can be used to produce petrochemical-grade benzane. Isomerization increases the octane of the stream by isomerizing the paraffins.

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    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    103 views6 pages

    Isomerization: P A R T 9

    Uploaded by

    Bharavi K S
    Major source of benzene in most refineries is the catalytic reformer. Reformate typically contributes 50 to 75 percent of the benzene in the gasoline pool. Reformation can be used to produce petrochemical-grade benzane. Isomerization increases the octane of the stream by isomerizing the paraffins.

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    Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

    ISOMERIZATION

    Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

    ISOMERIZATION

    Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

    Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

    CHAPTER 9.1

    UOP BENSAT PROCESS


    Dana K. Sullivan
    UOP LLC Des Plaines, Illinois

    The introduction of reformulated gasoline with mandated limits on benzene content has caused many refiners to take steps to reduce the benzene in their gasoline products. The major source of benzene in most refineries is the catalytic reformer. Reformate typically contributes 50 to 75 percent of the benzene in the gasoline pool. The two basic approaches to benzene reduction involve prefractionation of the benzene and benzene precursors in a naphtha splitter before reforming, postfractionation in a reformate splitter of the benzene after it is formed, or a combination of the two (Fig. 9.1.1). The benzene-rich stream must then be treated to eliminate the benzene by using extraction, alkylation, isomerization, or saturation (Figs. 9.1.2 and 9.1.3). If the refiner has an available benzene market, the benzene-rich stream can be sent to an extraction unit to produce petrochemical-grade benzene. Alkylation of the benzene may also be an attractive option if propylene is available, as in a fluid catalytic cracking (FCC) refinery. An isomerization unit saturates the benzene and also increases the octane of the stream by isomerizing the paraffins to a higher-octane mixture. Saturation in a stand-alone unit is a simple, low-cost option.

    FIGURE 9.1.1

    Fractionation for benzene reduction.

    9.3 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

    UOP BENSAT PROCESS 9.4


    ISOMERIZATION

    FIGURE 9.1.2 Prefractionation options.

    FIGURE 9.1.3

    Postfractionation options.

    PROCESS DISCUSSION
    The UOP* BenSat* process was developed to treat C5-C6 feedstocks with high benzene levels. Because almost all the benzene is saturated to cyclohexane over a fixed bed of catalyst, no measurable side reactions take place. Process conditions are moderate, and only a slight excess of hydrogen above the stoichiometric level is required. The high heat of reaction associated with benzene saturation is carefully managed to control the temperature rise across the reactor. Product yield is greater than 100 liquid volume percent (LV %), given the volumetric expansion associated with saturating benzene and the lack of any yield losses from cracking to light ends.
    *Trademark and/or service mark of UOP.

    Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

    UOP BENSAT PROCESS


    UOP BENSAT PROCESS

    9.5

    The product has a lower octane than the feed as a result of the conversion of the highoctane benzene into lower-octane cyclohexane. However, the octane can be increased by further processing the BenSat product in an isomerization unit, such as a UOP Penex unit (see Chap. 9.3).

    PROCESS FLOW
    The BenSat process flow is shown in Fig. 9.1.4. The liquid feed stream is pumped to the feed-effluent exchanger and to a preheater, which is used only during start-up. Once the unit is on-line, the heat of reaction provides the required heat input to the feed via the feedeffluent exchanger. Makeup hydrogen is combined with the liquid feed, and flow continues into the reactor. The reactor effluent is exchanged against fresh feed and then sent to a stabilizer for removal of light ends.

    CATALYST AND CHEMISTRY


    Saturating benzene with hydrogen is a common practice in the chemical industry for the production of cyclohexane. Three moles of hydrogen are required for each mole of benzene saturated. The saturation reaction is highly exothermic: the heat of reaction is 1100 Btu per pound of benzene saturated. Because the benzene-cyclohexane equilibrium is strongly influenced by temperature and pressure, reaction conditions must be chosen carefully. The UOP BenSat process uses a commercially proven noble metal catalyst, which has been used for many years for the production of petrochemical-grade cyclohexane. The catalyst is selective and has no measurable side reactions. Because no cracking occurs, no appreciable coke forms on the catalyst to reduce activity. Sulfur contamination in the feed reduces catalyst activity, but the effect is not permanent. Catalyst activity recovers when the sulfur is removed from the system.

    FIGURE 9.1.4

    BenSat process flow.

    Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

    UOP BENSAT PROCESS 9.6


    ISOMERIZATION

    FEEDSTOCK REQUIREMENTS
    Light straight-run naphthas must be hydrotreated to remove sulfur. Light reformates usually have very low sulfur contents, and so hydrotreating may not be required. Any olefins and any heavier aromatics, such as toluene, in the feed are also saturated. Table 9.1.1 shows typical feedstock sources and compositions. The makeup hydrogen can be of any reasonable purity and is usually provided by a catalytic reformer.

    COMMERCIAL EXPERIENCE
    The estimated erected cost (EEC) for a light reformate, fresh-feed capacity of 10,000 barrels per stream day (BPSD) at a feed benzene level of 20 percent by volume is $5.6 million. Estimated erected costs are inside battery limits, U.S. Gulf Coast open-shop construction (2002). The EEC consists of a materials and labor estimate; design, engineering, and contractors fees; overheads; and expense allowance. The quoted EEC does not include such off-site expenses as cost and site preparation of land, power generation, electrical substations, off-site tankage, or marine terminals. The off-site costs vary widely with the location and existing infrastructure at the specific site. In addition, off-site cost depends on the process unit. A summary of utility requirements is shown in Table 9.1.2. There are four BenSat units in operation. BenSat catalyst and technology are also used in four additional operating UOP Penex-Plus units.

    TABLE 9.1.1

    Typical Feed Compositions, LV % Light reformate

    Component C5 paraffins C5 naphthenes C6 paraffins C6 naphthenes C 7+ Benzene Total


    Note: LSR

    LSR 28 4 35 17 8 8 100
    light straight run.

    Light cut 29 0 34 3 16 18 100

    Heartcut 0 0 47 3 24 26 100

    TABLE 9.1.2

    Utilities 184 7400 (16.3) 7400 (16.3) 119.5 (526)

    Electric, kW Medium-pressure steam, kg/h (klb/h) Condensate,* kg/h (klb/h) Cooling water, m3/h (gal/min)
    *Quantity exported.

    Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

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