Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 13.2

UOP ETHERMAX PROCESS FOR MTBE, ETBE, AND TAME PRODUCTION

Steve Krupa, Jill Meister, and Charles Luebke
UOP LLC Des Plaines, Illinois

PROCESS DESCRIPTION
The Ethermax* process, licensed exclusively by UOP,* can be used to produce methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), or ethyl tertiary butyl ether (ETBE). This process combines the Hls fixed-bed etherification process with advanced RWD catalytic distillation technology from Koch-Glitsch, Inc. The combined technology overcomes reaction equilibrium limitations inherent in a conventional fixed-bed etherification process. The Ethermax process reacts tertiary olefins, such as isobutylene and isoamylene, over an acid resin in the presence of alcohol to form an ether. The reaction chemistry and unit operating conditions are essentially the same as those of a conventional ether process, such as the Hls MTBE process (Chap. 13.1), except that KataMax packing has been added to increase the overall conversion. KataMax packing represents a unique and proprietary approach to exposing a solid catalyst to a liquid stream inside a distillation column. The reactive distillation zone of the RWD column uses KataMax packing to overcome reaction equilibrium constraints by continuously fractionating the ether product from unreacted feed components. As the ether product is distilled away, the reacting mixture is no longer at equilibrium. Thus, fractionation in the presence of the catalyst promotes additional conversion of the reactants. Isobutylene conversions of 99 and 97 percent, respectively, for MTBE and ETBE are typical, and isoamylene conversions of up to 94 percent can be achieved economically with this process. These design specifications are typical for gasoline blending; however, practically any olefin conversion is achievable by designing a unit to accommodate individual refinery needs. For example, the Ethermax process can be designed to convert 99.9 percent of the isobutylene when butene-1 production is a design objective.

*Trademark and/or service mark of UOP. Trademark of Koch-Glitsch, Inc.

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UOP ETHERMAX PROCESS FOR MTBE, ETBE, AND TAME PRODUCTION 13.10
OXGENATES PRODUCTION TECHNOLOGIES

The flexibility of the Ethermax process provides refiners with many routes to increase oxygenate or octane levels in their gasoline pool. Existing MTBE units can be converted to TAME or ETBE production. Increases in throughput and olefin conversion are possible in an existing ether unit by revamping it to the Ethermax process. The revamp increases the oxygenate level of the gasoline pool, and the resulting octane improvement gives a refiner the flexibility to optimize gasoline production from other refinery processes.

PROCESS FLOW
The process flow for the Ethermax process is shown in Fig. 13.2.1. The majority of the reaction is carried out in a simple fixed-bed adiabatic reactor. The effluent from this reactor feeds the RWD column, where the ethers are separated from unreacted feed components. The bottoms from the RWD column are the MTBE, ETBE, or TAME product. The unreacted components move up the column and enter the catalytic section of the fractionator for additional conversion. The catalytic section of the RWD column uses KataMax packing to overcome reaction equilibrium constraints by simultaneously reacting the feed component and fractionating the ether product. The overhead from the RWD column is routed to the alcohol (either methanol or ethanol) recovery section. In this system, water is used to separate the alcohol from the hydrocarbon in a simple countercurrent extraction column, and a distillation column is used to recover the alcohol. The recovered alcohol is recycled to the reactor section. The hydrocarbon raffinate is generally sent downstream to an alkylation unit in the case of C4s and some of the C5s. Depending on the gasoline Reid vapor pressure (RVP) specification, the C5s may be blended directly into the gasoline pool.

FIGURE 13.2.1

Ethermax process.

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UOP ETHERMAX PROCESS FOR MTBE, ETBE, AND TAME PRODUCTION

UOP ETHERMAX PROCESS FOR MTBE, ETBE, AND TAME

13.11

YIELDS
The example in Table 13.2.1 represents oxygenate production from fluid catalytic cracking (FCC) olefins using the Ethermax process to separately process the C4 and C5 cuts. The TAME feed is assumed to be pretreated to saturate dienes.

OPERATING COST AND ECONOMICS

The estimated utilities for a 50,000 metric ton per annum (MTA) (1279 BPD) Ethermax unit producing MTBE and a 70,000 MTA (1729 BPD) Ethermax unit producing TAME, respectively, are given in Table 13.2.2. The 2002 estimated erected cost for an Ethermax unit to produce 50,000 MTA (1279 BPD) of MTBE is $8 million U.S. and $11.5 million U.S. to produce 70,000 MTA (1729 BPD) of TAME including the SHP, based on the inside battery limits of the process unit erected in the U.S. Gulf Coast.

ETHERMAX COMMERCIAL EXPERIENCE

The first Ethermax process unit was commissioned at the Hls AG, Marl, Germany, facility in March 1992. As of 2002, another 10 Ethermax process units have been placed onstream. These units process a wide variety of feedstocks from FCC, stream cracking, and dehydrogenation units. The performance of all operating units has exceeded representations. An additional 11 Ethermax units have been licensed. Together these units represent more than 7,925 kMTA (200,000 BPSD) of ethers capacity. An improved KataMax packing design was commercialized in 1996. The new design further improved the already superior hydraulic capacity of the KataMax packing while maintaining excellent pressure drop and mass-transfer characteristics.

TABLE 13.2.1

Oxygenate Production from Ethermax Process MTBE operation, MTA (BPD) TAME operation, MTA (BPD) 200,600 (5960)

Total FCC hydrocarbon feed Reactive components in the feed: Hydrocarbons: iC4 iC5 Alcohols: Methanol Ethers product: MTBE TAME
Note: MTA

174,800 (5632)

33,000 (1052) 18,200 (436) 50,000 (1279)

61,000 (1688) 21,500 (515) 70,000 (1729)

iso.

metric tons per annum; BPD 5 barrels per day; i

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UOP ETHERMAX PROCESS FOR MTBE, ETBE, AND TAME PRODUCTION 13.12
OXGENATES PRODUCTION TECHNOLOGIES

TABLE 13.2.2 Utilities for Ethermax Unit Producing MTBE and TAME (including SHP) Utilities Electric power, kWh Steam, MT/h (klb/h): Low-pressure Medium-pressure Condensate,* MT/h (klb/h) Cooling water, m3/h (gal/min) Fuel gas,* million kcal/h (million Btu/h)
*Denotes export. Note: MT/h metric tons per hour.

Ethermax for MTBE 177 7.9 (17.4) 7.9 (17.4) 52 (227)

Ethermax for TAME 277 2.7 (6.0) 11.1 (24.5) 13.8 (30.5) 119 (524) 0.4 (1.5)

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