Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 13.3

UOP OLEFIN ISOMERIZATION

Steve Krupa
UOP LLC Des Plaines, Illinois

INTRODUCTION
UOP developed olefin isomerization catalysts and process technology primarily for use in a fuel ethers complex where methyl tertiary butyl ether (MTBE) or tertiary amyl methyl ether (TAME) is the desired product. These ethers are reaction products from isoolefins while normal olefins are not reactive. Olefin isomerization significantly increases ether production since feedstocks typically have more nC4= than iC4=. While presented here integrated in an ethers complex, UOPs olefin isomerization processes can be used in any other application where conversion of normal olefins to branched olefins is needed or desirable. The idea of skeletal isomerization of normal olefins to isoolefins is not new. During the 1960s, UOP scientists, as well as others, worked on catalyst development based on chlorided alumina. However, these previous catalyst systems were not attractive because they showed poor stability and low selectivity. The increasing demand for oxygenates has resulted in a higher demand for isobutylene and isoamylene to be used in ether production. UOP began active research in 1989 for a skeletal olefin isomerization catalyst. The timing of this demand was fortunate because of the emergence of a number of new catalytic materials. The challenge was to develop a catalyst with high selectivity and stability. With its unique expertise in the development of new materials, UOP developed a proprietary catalyst for skeletal isomerization of light normal olefins. The catalyst was further improved and then successfully produced in a commercial-scale manufacturing trial run.

DESCRIPTION OF THE PENTESOM PROCESS

The UOP* Pentesom* process isomerizes normal C5 olefins to reactive isoamylene for conversion to TAME. This unit, coupled with an ethers unit, such as the Ethermax* process (Chap. 13.2), maximizes the production of TAME derived from fluid catalytic cracking (FCC) unit C5 olefins. The high-conversion Pentesom unit normally can increase the

*Trademark and/or service mark of UOP.

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TAME production from an FCC unit by 1.7 times that of the stand-alone TAME Ethermax unit. The Pentesom-Ethermax flow scheme consumes more than 80 percent of the available C5 olefins in a typical FCC feed stream. This consumption compares to only about 50 percent C5 olefin utilization with stand-alone TAME production. UOPs analysis has shown that, in most cases, operating the Pentesom unit on a oncethrough basis by adding a second Ethermax unit downstream of the Pentesom unit is preferable to recycling the Pentesom effluent to a single Ethermax unit. The block flow diagram of this flow scheme is shown in Fig. 13.3.1. The primary benefit of this flow scheme is a savings in utilities. The FCC unit has a substantial amount of saturate unreactive C5s contained with the C5 olefins. When the Ethermax-Pentesom units are operated in a recycle mode, the resulting buildup of normal paraffins consumes both utilities and capacity that are not directed toward TAME production. The normal paraffins must be purged from the recycle loop by a bleed, which also results in a loss of normal pentenes from TAME production. Operation in a once-through flow scheme eliminates these concerns.

Pentesom Process Flow The Pentesom flow scheme consists of a single reactor containing a high-activity molecular-sieve-based catalyst (Fig. 13.3.2). The Ethermax effluent passes through a fired heater and is combined with a small amount of hydrogen before entering the single, fixed-bed Pentesom reactor. The reactor effluent is cooled and condensed before entering a separator. The separator overhead stream, which is rich in hydrogen, is compressed and recycled to the Pentesom reactor. A small amount of makeup hydrogen is added to the recycle stream. Separator bottoms are routed to a stripper. Stripper bottoms are sent to a second Ethermax unit for additional TAME production. No feed pretreatment other than that required for the Ethermax unit is required for the Pentesom process. The catalyst operates for 1 year between regenerations. The regeneration is normally conducted in situ using the existing process equipment. No additional regeneration equipment is needed.

DESCRIPTION OF THE BUTESOM PROCESS

The Butesom* process is UOPs C4 olefin isomerization process. The process isomerizes normal butenes to isobutylene, which can then be further converted to MTBE. The
*Trademark and/or service mark of UOP.

FIGURE 13.3.1

Typical FCCU C5 processing scheme.

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FIGURE 13.3.2 UOP Pentesom process.

Butesom unit is operated in a recycle mode with an ethers unit, such as UOPs Ethermax process (Chap. 13.2), for MTBE production. The Butesom-Ethermax flow scheme is targeted for streams rich in C4 olefins and low in paraffins. Such a stream is that available from naphtha-based steam crackers. In these situations, the raffinate is typically a relatively low-value product because no other conversion processes are available. The olefin utilization for MTBE in these cases is typically less than 30 percent. The Butesom-Ethermax flow scheme increases olefin utilization to 80 percent. The feedstock from the FCC unit contains a high saturate C4 concentration, which is normally not a good fit for a Butesom unit. The primary reason that the Butesom unit is more effective on high-olefin feedstocks is that the conversion of normal butene to isobutylene is equilibrium-limited to 40 to 50 percent under normal operating conditions. A recycle operation is used to achieve higher overall conversion of n-butene above the equilibrium limit. However, the high paraffin concentrations present in FCC feedstocks require a substantial bleed on the recycle loop to purge the paraffins. The recycle bleed drags butenes out of the flow scheme, thereby reducing the availability of butenes for conversion to MTBE.

Butesom Process Flow A simplified Butesom flow scheme is shown in Fig. 13.3.3. This simple unit uses a molecular-sieve-based catalyst and swing reactors. The Ethermax effluent passes through a combined feed exchanger and fired heater before entering one of the swing fixed-bed Butesom reactors. The reactors are operated in a swing mode with one reactor on-line and the other in regeneration. The reactor effluent is exchanged with the fresh feed in the combined feed exchanger and cooled before being compressed and condensed in the effluent compressor system. The liquid is then pumped back to the Ethermax unit for conversion to

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MTBE. The small amount of light ends produced in the Butesom unit are removed in the Ethermax unit.

Regeneration Section Unlike the UOP C5 skeletal isomerization system, all C4 skeletal isomerization catalyst systems have limited stability and require frequent regenerations. During the process cycle, a progressive accumulation of coke on the catalyst occurs. If the process cycle were extended significantly without regeneration, the coke deposited would cause a gradual decrease in catalyst performance. Therefore, the regeneration step is critical to the overall process economics. The Butesom process provides a regeneration system that is simple and low-cost. The regeneration consists of a simple carbon burn to remove the coke on the catalyst. Because the burn is conducted in the reactor, less regeneration equipment is required. Consequently, the valving and maintenance problems associated with moving catalyst are eliminated. The regeneration sequence is as follows:

Reactor isolation Evacuation and N2 pressure-up Carbon burn Evacuation and N2 pressure-up Reactor on-line

The evacuation and pressure-up steps are accomplished by a common single-stage steam ejector. Purge gas is minimized by designing the system so that only the reactor itself needs to go through the evacuation and purge steps. The carbon burn is the only catalyst regeneration step required to restore the catalyst activity; no promoters or special activators are used on or with the catalyst. The carbon burn is controlled simply by regu-

FIGURE 13.3.3 UOP Butesom process.

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lating the oxygen content and temperature in the burn zone. Utility air is used as the oxygen source. No costly dryers or special utilities are required.

ECONOMICS
The Pentesom-Ethermax process flow scheme increases the typical FCC TAME production by about 1.7 times compared to a stand-alone Ethermax unit for TAME production. The capital cost for an Ethermax-Pentesom-Ethermax complex built on the U.S. Gulf Coast in 1995 and producing 103,000 metric tons per year (MTA) [2500 barrels per day (BPD)] of TAME from FCC-derived feed is approximately $21 million U.S. A Butesom-Ethermax complex processing an FCC feedstock can typically produce about 1.7 times the production of a stand-alone Ethermax unit. The estimated 1995 U.S. Gulf Coast erected cost for a complex to produce 86,800 MTA (2200 BPD) of MTBE is $23 million U.S.

COMMERCIAL EXPERIENCE
The Butesom and Pentesom processes are offered for commercial license. The catalyst systems used in the Pentesom and Butesom processes were under development for almost 5 years. Pilot-plant tests included process variable studies as well as contaminant studies. The catalyst was tested under commercial conditions and exposed to multiple regeneration cycles. A commercial manufacturing test run was successfully conducted. The equipment and operating conditions for the Butesom and Pentesom processes were well within the normal refining engineering boundaries. The Butesom and Pentesom designs draw on the expertise gained in these commercial runs as well as on the experience gained in more than 80 years of process commercialization.

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UOP OLEFIN ISOMERIZATION

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