Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 9.2

UOP BUTAMER PROCESS

Nelson A. Cusher
UOP LLC Des Plaines, Illinois

INTRODUCTION
The first successful efforts in the research and development of catalytic systems for the isomerization of normal paraffins came in the early 1930s. The requirement for high-octane aviation gasoline during World War II accelerated the application of early isomerization research. Light olefinic hydrocarbons were available from the newly developed fluid catalytic cracking (FCC) process and from other mainly thermal operations. These olefinic hydrocarbons could be alkylated with isobutane (iC4) to produce a high-octane gasoline blending component. However, the supply of isobutane from straight-run sources and other refinery processing was insufficient, and a new source of supply had to be found. Isobutane produced from the new normal paraffin isomerization process met that need. The first commercial butane isomerization unit went on-stream in late 1941. By the end of the war, 38 plants were in operation in the United States and 5 in allied countries for a total capacity of approximately 50,000 barrels per stream day (BPSD). Five principal isomerization processes, including one developed by UOP, were used in the United States. All were based on Friedel-Crafts chemistry and used aluminum chloride in some form. The wartime units fulfilled the needs of the time. However, despite many improvements, the units remained difficult and costly to operate. Corrosion rates were excessive, plugging of catalyst beds and equipment was common, and catalyst consumption was high. The units were characterized by high maintenance and operating costs and low onstream efficiency. The introduction of UOP*s Platforming* process in 1949 and the rapid spread of such catalytic reforming over dual-functional catalysts in the 1950s served to focus attention on the development of similar catalysts for paraffin isomerization. The term dual functional refers to the hydrogenation and controlled-acidity components of a catalyst. Isomerization was known to be one of several reactions that occurred during catalytic reforming, and so isolating this reaction for use with feeds that did not require any of the other reactions was a natural next step. Although the earlier of these dual-functional catalysts eliminated many of the shortcomings of the wartime aluminum chloride catalyst systems, they required relatively high
*Trademark and/or service mark of UOP.

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UOP BUTAMER PROCESS 9.8

ISOMERIZATION

operating temperatures. At these temperatures, unfavorable equilibriums limited per-pass conversion. Further research was conducted, and in 1959, UOP made available to the industry a butane isomerization process, UOPs Butamer* process, that used a highly active, low-temperature hydroisomerization catalyst capable of achieving butane conversion at temperature levels equivalent to the wartime Friedel-Crafts systems without the attendant corrosion or sludge formations. Industry acceptance of the UOP process was rapid, and in late 1959, the first Butamer unit, the first commercial butane isomerization unit to use a low-temperature, dual-functional catalyst system, was placed on-stream on the United States West Coast.

PROCESS DESCRIPTION
The Butamer process is a fixed-bed, vapor-phase process promoted by the injection of trace amounts of organic chloride. The reaction is conducted in the presence of a minor amount of hydrogen, which suppresses the polymerization of olefins formed as intermediates in the isomerization reaction. Even though the chloride is converted to hydrogen chloride, carbon steel construction is used successfully because of the dry environment. The process uses a highactivity, selective catalyst that promotes the desired conversion of normal butane (nC4) to isobutane at low temperature and, hence, at favorable equilibrium conditions. Regardless of the iC4 content of the feed, the butane fraction leaving the unit contains approximately 60 percent by volume of iC4. Therefore, to obtain optimum plant performance, the refiner wants to charge a butane cut containing the highest practical content of nC4. The catalytic reaction is highly selective and efficient and results in a minimum of hydrocracking to light ends or the formation of heavy coproduct. Volumetric yield of iC4 product based on an nC4 feed typically approximates slightly more than 100 percent.

PROCESS CHEMISTRY
Isomerization by dual-functional catalysts is thought to operate through an olefin intermediate. The formation of this intermediate is catalyzed by the metallic component, which is assumed for this discussion to be platinum: CH3 CH2 CH2 CH3 CH3
Pt

CH2

CH

CH2

H2

(9.2.1)

This reaction is, of course, reversible, and because these catalysts are used under substantial hydrogen pressure, the equilibrium is far to the left. However, the acid function (H+A ) of the catalyst consumes the olefin to form a carbonium ion and thus permits more olefin to form despite the unfavorable equilibrium: CH3 CH2 CH CH2 H A CH3 CH2 CH CH3 A (9.2.2)

The usual rearrangement ensues: CH3 | C CH3

CH3

CH2

CH

CH3 CH3

(9.2.3)

*Trademark and/or service mark of UOP.

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UOP BUTAMER PROCESS

UOP BUTAMER PROCESS

9.9

The isoolefin is then formed by the reverse analog of Eq. (9.2.2): CH3 CH3 C CH3 CH3 CH3 C CH2 (9.2.4)

The isoparaffin is finally created by hydrogenation: CH3 CH3 C CH2

2

CH3 CH3
Pt

CH

CH3

(9.2.5)

PROCESS VARIABLES
The degree of isomerization that occurs in the Butamer process is influenced by the following process variables. Reactor Temperature The reactor temperature is the main process control for the Butamer unit. An increase in temperature increases the iC4 content of the product toward its equilibrium value and slightly increases cracking of the feed to propane and lighter. Liquid Hourly Space Velocity (LHSV) An increase in LHSV tends to decrease the iC4 in the product at a constant temperature when other conditions remain the same. Hydrogen-to-Hydrocarbon Ratio (H2/HC) The conversion of nC4 to iC4 is increased by reducing the H2/HC ratio; however, the hydrogen effect is slight over the usual operating range. Significant capital savings do result when the H2/HC ratio is low enough to eliminate the recycle hydrogen compressor and product separator. UOPs standard (and patented) design calls for a H2/HC ratio of 0.03 molar and allows operation with once-through hydrogen. Pressure Pressure has no effect on equilibrium and only a minor influence on the conversion of normal butane to isobutane.

PROCESS CONTAMINANTS
Water poisons the Butamer catalyst. A simple but effective molecular-sieve drying system is used on unit hydrocarbon and gas feeds. Sulfur is a temporary poison that inhibits catalyst
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UOP BUTAMER PROCESS 9.10

ISOMERIZATION

activity. The effect of sulfur entering the reaction system is to lower the conversion per pass of normal butane to isobutane. Butamer catalyst exposed to sulfur essentially recovers its original activity when the sulfur is eliminated from the feed. Also, the effect of sulfur on the Butamer system is minimal because the molecular-sieve feed dryers are also capable of economically removing this material from typical butane fractions. Should a potential feed of relatively high sulfur content be encountered, the bulk of this content would be mercaptan sulfur that is readily removed by simple caustic extraction, such as UOPs Merox* process. The residual sulfur remaining after extraction would then be removed by the feed-drying system of the molecular sieve. Another catalyst poison is fluoride, which also degrades the molecular sieves used for drying. Butamer feeds derived from an HF alkylation unit contain such fluorides, which are removed by passing them over a hot bed of alumina. The proper design of simple feed-pretreatment facilities effectively controls contaminants and minimizes catalyst consumption.

ISOMERIZATION REACTORS
One characteristic of the Butamer process is that catalyst deactivation begins at the inlet of the first reactor and proceeds slowly as a rather sharp front downward through the bed. The adverse effect that such deactivation can have on unit on-stream efficiency is avoided by installing two reactors in series. Each reactor contains 50 percent of the total required catalyst. Piping and valving are arranged to permit isolation of the reactor containing the spent catalyst while the second reactor remains in operation. After the spent catalyst has been replaced, the relative processing positions of the two reactors are reversed. During the short time when one reactor is off-line for catalyst replacement, the second reactor is fully capable of maintaining continuous operation at design throughput, yield, and conversion. Thus, run length is contingent only on the scheduling of shutdown for normal inspection and maintenance. In addition to the advantages associated with maximizing on-stream efficiency, a tworeactor system effectively reduces catalyst consumption. Reactors are typically sized so that by the time approximately 75 percent of the total catalyst bed is spent, isomerization decreases to an unacceptable level, and some catalyst replacement is needed. In a singlereactor unit, 25 percent of the original catalyst load, although still active, is discarded when the reactor is unloaded. In a two-reactor system, no active catalyst need be discarded because 50 percent replacement is made when catalyst in the first reactor has been spent. Catalyst utilization is thus 100 percent. The choice of a single-reactor or a two-reactor system depends on the particular situation and must be made by evaluating the advantages of essentially continuous operation and increased catalyst utilization against the expense of the somewhat more costly tworeactor installation. Both systems are commercially viable, and Butamer plants of both types are in operation.

PROCESS FLOW SCHEME

The overall process-flow scheme for the Butamer system depends on the specific application. Feed streams of about 30 percent or more iC4 are advantageously enriched in nC4 by charging the total feed to a deisobutanizer column. Feeds that are already rich in nC4 are
*Trademark and/or service mark of UOP.

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UOP BUTAMER PROCESS

UOP BUTAMER PROCESS

9.11

FIGURE 9.2.1 UOP Butamer process.

charged directly to the reactor section. A simplified flow scheme is depicted in Fig. 9.2.1. An nC4 concentrate, recovered as a deisobutanizer sidecut, is directed to the reactor section, where it is combined with makeup hydrogen, heated, and charged to the Butamer reactor. Reactor effluent is cooled and flows to a stabilizer for removal of the small amount of light gas coproduct. Neither a recycle gas compressor nor a product separator is required because only a slight excess of hydrogen is used over that required to support the conversion reaction. Stabilizer bottoms is returned to the deisobutanizer, where any iC4 present in the total feed or produced in the isomerization reactor is recovered overhead. Unconverted nC4 is recycled to the reactor section by way of the deisobutanizer sidecut. The system is purged of pentane and heavier hydrocarbons, which may be present in the feed, by withdrawing a small drag stream from the deisobutanizer bottoms. The Butamer process may also be incorporated into the design of new alkylation plants or into the operation of existing alkylation units. For this type of application, the inherent capabilities of the iC4 fractionation facilities in the alkylation unit may be used to prepare a suitable Butamer feed with a high nC4 content and to recover unconverted nC4 for recycle. The major historical use of the Butamer process has been the production of iC4 for the conversion of C3 and C4 refinery olefins to high-octane alkylate. A more recent demand for iC4 has developed in conjunction with the manufacture of methyl tertiary butyl ether (MTBE), which is a high-octane gasoline blending component particularly useful in reformulated gasolines. Isobutane is dehydrogenated to isobutylene and then made into MTBE. Unconverted butenes and nC4 are recycled as appropriate to achieve essentially 100 percent conversion of the feed butanes to MTBE.

COMMERCIAL EXPERIENCE
More than 70 UOP Butamer units have been commissioned to date, and 5 others are in engineering design or construction. Product design capacities range from 800 to more than 30,000 BPSD. Typical yields and investment and operating costs are shown in Tables 9.2.1, 9.2.2, and 9.2.3.
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UOP BUTAMER PROCESS 9.12 TABLE 9.2.1 feed Feedstock Propane Isobutane n-butane Isopentane n-pentane Total Chemical hydrogen (100% H2 purity) Products Isobutane: Propane Isobutane n-butane Total Heavy-end by-product: Isobutane n-butane Isopentane n-pentane Total Light gas: Methane Ethane Propane Total 978 104,190 3,922 109,089 69 2,702 1,058 978 4,807 252 357 541 1,150 37 3540 128 3705 2 89 32 30 153 39,300 29,800 31,300 100,400 0.85 90.60 3.41 94.86 0.06 2.35 0.92 0.85 4.18 0.22 0.31 0.47 1.00 978 29,325 82,282 1,805 610 115,000 65.6 37 996 2693 56 18 3800 55,600 0.85 25.50 71.55 1.57 0.53 100.00 0.04 Estimated Yields* MTA m3/h BPSD SCF/day wt % on
ISOMERIZATION

*Basis: Feedstock type: field butane. Hydrogen requirement: does not include that dissolved in the separator liquid. Isobutane purity: 96.5 vol %. Note: MTA metric tons per annum; BPSD barrels per stream day; SCF standard cubic feet.

TABLE 9.2.2 Estimated Investment Requirements for Butamer Unit with Deisobutanizer Column* $ U.S. Materials and labor Design, engineering, and contractors fees Estimated erected cost Allowance for catalyst, chemicals, and noble metal on catalyst 10,400,000 4,500,000 14,900,000 280,000

*Basis: Feed rate: 115,000 MTA (3,800 BPSD). U.S. Gulf Coast erection to UOP standards exclusive of off-site costs, third quarter 2001. Allowance for catalyst and chemicals reflects current prices FOB point of manufacture.

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UOP BUTAMER PROCESS

UOP BUTAMER PROCESS

9.13

TABLE 9.2.3

Estimated Operating Requirements* Butamer unit 300 5.0 11.1 16.3 35.9 35 (155) $ U.S. per stream day 600

Utility requirements Power, kW Medium-pressure steam: At 14.1 kg/cm2, 1000 kg/h At 200 lb/in2 gage, 1000 lb/h Low-pressure steam: At 3.5 kg/cm2, 1000 kg/h At 50 lb/in2 gage, 1000 lb/h Cooling water, m3/h (gal/min) Total Catalyst and chemical consumption, $ U.S. per stream day Labor allowance/shift: Operator Helper

Deisobutanizer 200

936

89 (390)

2153 77 3766

523

523 0.50 0.50

*Basis: Feed rate 115,000 MTA (3800 BPSD). Utility cost basis: electric power $0.05/kW; medium-pressure steam $3.50/klb; low-pressure steam $2.50/klb. Maintenance allowance 3% of erected cost.

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UOP BUTAMER PROCESS

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