Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

13

OXYGENATES PRODUCTION TECHNOLOGIES

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OXYGENATES PRODUCTION TECHNOLOGIES

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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 13.1

HLS ETHERS PROCESSES

Steve Krupa and Jill Meister
UOP LLC Des Plaines, Illinois

INTRODUCTION
During the early 1990s, the oxygenate portion of the gasoline pool was the fastest-growing gasoline component, and the majority of this growth was in methyl tertiary butyl ether (MTBE). The major reasons for this growth were generally considered to be environmental concerns and octane upgrades. Countries such as the United States, Korea, and Taiwan mandated the use of oxygenates in gasoline to promote cleaner-burning fuels. Lead phasedown programs, the introduction of midgrade and higher-octane premium gasolines, and newer, more sophisticated car engines all contributed to a steadily increasing demand for higher-quality gasoline and thus a continuing need to increase the octane of the refinery gasoline pool. In the late 1990s regulators in the United States passed legislation requiring the phaseout of MTBE from many markets in the early 2000s, due to numerous instances of groundwater contamination with MTBE. The major cause of the contamination is leaking underground storage tanks and pipelines and limited biodegradability. Some people have a very low taste threshold of 10 ppb MTBE in H2O. Very few new ether units for fuels applications have been constructed since the U.S. action. By 2002 many U.S. producers stopped MTBE production and were considering alternative technology to consume isobutene by reusing MTBE plant equipment (see UOP InAlk process). An important source of MTBE, as well as other ethers, is the refinery. In 1994, installed refinery MTBE capacity of more than 5.57 million metric tons per annum (MTA) [129,000 barrels per stream-day (BPSD)] represented about 28 percent of the worldwide MTBE production. Other major sources of MTBE production are from the dehydrogenation of isobutene (see Chap. 5.1), as a by-product from propylene oxide production, and from naphtha cracker C4s. Although MTBE is the most common ether, it is not the only ether used in gasoline blending today. Tertiary amyl methyl ether (TAME), ethyl tertiary butyl ether (ETBE), and diisopropyl ether (DIPE) are also used as gasoline blending ethers. Table 13.1.1 provides a list of the gasoline blending properties of ethers being used in gasoline pools. In addition to providing a gasoline oxygenate source, these ethers have excellent research and motor blending octanes.

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HLS ETHERS PROCESSES 13.4 TABLE 13.1.1

OXYGENATES PRODUCTION TECHNOLOGIES

Refinery Oxygenates Blending octane Blending RVP M)/2 109 105 105 110 kg/cm2 0.560.70 0.280.35 0.210.35 0.210.35 lb/in2 810 45 35 35 Oxygen, wt % 18.2 15.7 15.7 15.7
motor

Ethers MTBE DIPE TAME ETBE

RONC 118 112 111 117

MONC 100 98 98 102

(R

Note: RVP Reid vapor pressure; RONC research octane number clear; MONC octane number clear; (R M)/2 (RONC)/2 (sometimes referred to as road octane).

Ethers are generally favored over alcohols in gasoline blending for two reasons: they have a very low solubility in water compared to alcohols, and they have a low blending vapor pressure compared to alcohols.

HLS ETHERS PROCESS FOR MTBE, ETBE, AND TAME

The Hls ethers processes for MTBE, TAME, ETBE, and tert-amyl ethyl ether (TAEE), formerly colicensed by UOP and Hls AG, are now licensed exclusively from UOP in Des Plaines, Illinois, as part of the UOP Ethermax process technology. This process can be used to produce the ethers for gasoline blending from olefin feedstocks available within a refinery. Depending on the type of hydrocarbon and alcohol feed, the following etherification reactions take place: CH2 CH2 CH3CH C(CH3)
Isobutylene
2

CH3OH (CH3)3 C O CH3

Methanol MTBE

(13.1.1) (13.1.2) (13.1.3)

C(CH3)2 C(CH3)2

CH3CH2OH (CH3)3 C O CH2CH3

Ethanol ETBE

Isobutylene

CH3OH CH3CH2 (CH3)2 C O CH3

Methanol TAME

Isoamylene

The reactions proceed in the liquid phase at mild conditions in the presence of a solid acidic catalyst. The catalyst typically is a sulfonic ion-exchange resin. The reaction temperature is kept low and can be adjusted over a fairly broad range. Higher temperatures are possible, but excessive temperatures are not recommended because resin fouling from polymers can occur. Around 130C (266F), sulfonic ion-exchange resins become unstable. Operation in the lower temperature range ensures stable operation and long catalyst life. The reaction of an isoolefin with alcohol is conducted in the presence of a small excess of alcohol relative to that required for the stoichiometric reaction of the isoolefin contained in the hydrocarbon feed. Operation with a small excess of alcohol has a number of advantages and practically no drawbacks because any excess alcohol is recovered and recycled. Some of the advantages are that

The equilibrium is displaced toward the production of ether to favor higher per-pass conversion. Production of high-octane ether is maximized, and production of lower-octane oligimers is minimized.

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HLS ETHERS PROCESSES

HLS ETHERS PROCESSES

13.5

Process temperature is more efficiently and securely controlled.

In the absence of a small excess of alcohol, isoolefin dimerization, also exothermic, can take place rapidly. This reaction can result in a sharp temperature rise in the resin bed. Such an increase causes irreversible catalyst fouling, and catalyst destruction can occur if the temperature rise is excessive. Under proper conditions, the etherification reaction is nearly 100 percent selective except for minor side reactions resulting from the presence of certain feed impurities. Water contained in the feed results in equivalent amounts of tertiary butyl alcohol (TBA) in the MTBE or ETBE product. Water in isoamylene feed yields tertiary amyl alcohol (TAA) in the TAME product. In small quantities, these alcohol by-products are unimportant. They need not be separated from the ether product because they have high octane values and can be used as gasoline blending agents. Either a one-stage or two-stage Hlls design can be used for MTBE, TAME, or ETBE production. A simplified flow diagram of the single- and two-stage designs is shown in Figs. 13.1.1 and 13.1.2, respectively. The two-stage unit produces higher conversion levels but costs more compared to the one-stage design. Because of the lower cost, the Hlls one-stage design is by far the most common inside the refinery. Two-stage units are typically built only when extremely high-purity raffinate is required, such as in butene-1 production, or when the raffinate is used in a recycle operation. Typical one-stage olefin conversions are shown in Table 13.1.2.

PROCESS FLOW
The fresh hydrocarbon feed must be treated in a water wash if it comes from a fluid catalytic cracking (FCC) unit. The treatment step is needed to remove basic nitrogen compounds, which are catalyst poisons. This procedure is not necessary if the feed comes from either a steam cracker or a UOP Oleflex* unit. In the case of TAME production, diolefins must also be removed in a hydrogenation unit (see Chap. 8.2). Figure 13.1.1 is a simplified single-stage process flow diagram. The clean fresh feed is mixed with fresh and recycled alcohol and charged to the reactor section. The reactor can be a tubular reactor, or more typically, two adiabatic reactors with recycle are used. The majority of the reaction occurs in the first reactor. The second reactor completes the reaction of isoolefins to ether. Cooling between reactors is required to maximize the approach to equilibrium in the second reactor. The product from the reactor section primarily contains ether, excess alcohol (methanol or ethanol), and unreacted C4 or C5 hydrocarbons. This stream is sent to a fractionation column, where high-purity MTBE, ETBE, or TAME is recovered from the bottoms. The unreacted hydrocarbon, typically referred to as the raffinate stream, and alcohol are taken off the top of the fractionator. Before it leaves the unit, the raffinate is water-washed to remove excess alcohol. The water-alcohol mixture from the water wash is fractionated in the alcohol recovery section. The recovered alcohol is recycled back to the reactor, and the water is recycled back to the water wash.

YIELDS
The yields in Table 13.1.3 are representative of the oxygenate production from FCC olefins using a single-stage Hlls process to separately process the C4 and C5 cuts. The TAME process feed is assumed to be pretreated in a diene saturation unit.
*Trademark and/or service mark of UOP.

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HLS ETHERS PROCESSES

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FIGURE 13.1.1

Hls MTBE, ETBE, and TAME processsingle-stage unit.

HLS ETHERS PROCESSES

HLS ETHERS PROCESSES

13.7

FIGURE 13.1.2

Hls MTBE, ETBE, and TAME processtwo-stage unit.

TABLE 13.1.2 Olefin feedstocks Isobutylene Isoamylene

Typical One-Stage Olefin Conversions MTBE 9697% TAME 6570% ETBE 8688%

ECONOMICS AND OPERATING COSTS

The estimated erected cost of a UOP-designed single-stage Hls MTBE process unit for the production of 60,000 MTA (1520 BPD) of MTBE in 1995 was $8.2 million. This capital estimate is for an inside-battery-limits unit erected on the U.S. Gulf Coast. The utility requirements for a 60,000 MTA (1520 BPD) MTBE unit and 75,000 MTA (1825 BPD) TAME, respectively, are estimated in Table 13.1.4. For an update on project economics and utilities, see the UOP Ethermax technology section.

COMMERCIAL EXPERIENCE
Twenty Hls MTBE units have been brought on-stream. The first unit started up in 1976 in Marl, Germany. Operating plant capacities range up to about 600,000 MTA (15,200 BPSD) of MTBE. The units cover the entire range of feed compositions, product qualities, isobutylene conversions, and end uses for MTBE. Five Hls MTBE units were revamped to Hls ETBE operation in the late 1990s and early 2000s.

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HLS ETHERS PROCESSES 13.8 TABLE 13.1.3

OXYGENATES PRODUCTION TECHNOLOGIES

Ethers Production from Single-Stage Units Hls MTBE process, MTA (BPD) Hls ETBE process, MTA (BPD) 264,100 (8437) Hls TAME process, MTA (BPD) 305,700 (8971)

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

264,100 (8437)

39,600 (1247) 22,000 (522)

39,600 (1247) 28,100

76,500 (2167) 23,700 (562)

(666)

60,000 (1520)

62,000 (1573) 75,000 (1825)

iso.

metric tons per annum; BPD

barrels per day; i

TABLE 13.1.4 Utilities

Utility Requirements MTBE 129 7.2 (15.8) 7.2 (15.8) 64 (282) TAME 160 12.0 (26.4) 12.0 (26.4) 63 (278)

Power, kWh Low-pressure steam, MT/h (klb/h) Condensate,* MT/h (klb/h) Cooling water, m3/h (gal/min)
*Denotes export. Note: MT/h metric tons per hour.

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