Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.2

SELECTIVE HYDROGENATION PROCESSES

Beth McCulloch, Charles Luebke, and Jill Meister
UOP LLC Des Plaines, Illinois

The presence of dienes and acetylenes in light olefinic streams is often undesirable, and these reactive contaminants must be removed from the olefinic streams without affecting the nature or concentration of the olefins. The dienes and acetylenes are typically removed by selective hydrogenation to the corresponding monoolefins. Light olefin streams are produced by steam cracking, dehydrogenation of C3/C4 paraffins, or fluid catalytic cracking (FCC). There are a number of processes that selectively remove reactive components such as acetylenes or dienes from olefinic streams.15

INTRODUCTION
Hydrogenation of dienes and acetylenic compounds can be accomplished selectively in the presence of monoolefins by using mild hydrogenation conditions. Chemische Werke Hls developed the concept of selective hydrogenation in 1963. The first Hls Selective Hydrogenation Process (SHP) was commercialized in 1980. The unit processed 160 kMTA of C4 feed derived from a steam cracking unit. The SHP unit is applicable to all C3C5 feedstocks including sulfur-containing feeds from FCC units. The selectivity of the hydrogenation reaction is dependent on the nature of the catalyst and the operating conditions. Hydrogenation is carried out at mild conditions with a slight stoichiometric excess of hydrogen. The Hls SHP unit is licensed by UOP for the selective hydrogenation of butadiene to butenes, for propadiene and methylacetylene to propene, and for pentadienes to pentenes. UOP also offers the KLP process to selectively remove acetylenes from crude butadiene feedstocks.

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SELECTIVE HYDROGENATION PROCESSES 8.26

HYDROTREATING

THE KLP PROCESS

1,3-Butadiene is an important petrochemical intermediate recovered from the C4 fraction of a naphtha steam cracking unit. The C4 cut from a steam cracking unit contains up to 60 percent butadiene and also small amounts of C4 acetylenes that need to be separated from the main butadiene product. Acetylenic compounds, such as vinyl acetylene and ethyl acetylene, can be selectively removed using the KLP process prior to butadiene extraction.6,7 The KLP process is used to convert essentially 100 percent of the alphaacetylenes to monoolefins and butadiene. The KLP process is highly selective, and there is no yield loss of butadiene; in fact, there may be a slight yield gain. With acetylenes no longer present, the extraction of butadiene can be accomplished in a single-stage unit. The KLP process can be readily integrated into existing extraction units and allows for a capacity increase or debottlenecking of the existing extraction unit. A process flow diagram of the KLP process integrated with a butadiene extraction unit is shown in Fig. 8.2.1. The extracted butadiene is very high-purity, with acetylene levels typically less than 10 ppm. The raffinate I stream still contains low levels of butadiene that may be removed by the SHP unit.

KLP Reactors Butadiene

H2 C4 Cut LP Steam
FIGURE 8.2.1 The KLP process.

Single Extraction

Raffinate-1

THE SHP UNIT

The removal of butadiene from a C4 olefin-rich stream can be readily accomplished using the SHP unit with a noble or non-noble-metal catalyst system. The process has been optimized to minimize losses of 1-butene through either hydrogenation or isomerization and to achieve levels of residual butadiene to as low as 10 ppm. Hls has successfully developed two modes of operation using a non-noble-metal or a noble metal catalyst depending on the processing objectives. In the first mode of operation, the dienes and acetylenes are selectively hydrogenated, and the n-butene isomer concentration moves toward the equilibrium concentration. At the low temperatures used in the SHP unit, the 2-butene is thermodynamically favored. This mode of operation is desirable for preparation of HF catalyzed alkylation feedstocks. The butene isomerization that occurs over the SHP catalyst will increase the ratio of 2-butene to 1-butene typically from about 2 to 8. The increased 2-butene content will increase alkylate octane by up to two research numbers in HF catalyzed alkylation units. In the second mode of operation the isomerization activity is suppressed while hydrogenation activity is maintained. This mode of operation is desirable for the production of high-purity comonomer-grade 1-

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SELECTIVE HYDROGENATION PROCESSES

SELECTIVE HYDROGENATION PROCESSES

8.27

Light Ends Recovery

Reactor

Stripper

Hydrogen Reactor Recycle Alkylation Unit Olefin Feed

FIGURE 8.2.2 Hls Selective Hydrogenation Process flow diagram.

butene. In addition, reducing the diene content in HF and H2SO4 catalyzed alkylation units results in lower acid consumption and increased alkylate yield. A flow diagram for the SHP unit is shown in Fig. 8.2.2. The feed is combined with hydrogen at near stoichiometric ratios to the diene and acetylene content of the feed. Hydrogenation then takes place in a fixed-bed reactor. In cases where the diene concentration of the feed is high, a portion of the reactor effluent is recycled. The hydrogen leaving the reactor is at a very low concentration and does not require removal unless a downstream process is sensitive to noncondensable gases. A Hls SHP unit is easy to operate, and minimal utilities are required, especially if the feed and hydrogen are both available at suitable pressure. Table 8.2.1 illustrates the two different modes of operation. The same feedstock is used with the same hydrogen addition rate and space velocity. In the first mode, good hydrogenation is achieved with a high level of isomerization from 1-butene to 2-butene. In the second mode, the SHP unit is optimized for the production of 1-butene. Essentially complete removal of dienes and acetylenes is achieved in either case, and there is no loss of n-butenes. In refineries, light olefin streams are produced by FCC units. Removal of the acetylenes and dienes from C3C5 streams is readily achieved with the SHP unit. For example, polymergrade propylene requires less than 5 wt ppm of dienes and acetylenes to meet specifications. The C4 and C5 steams derived from an FCC unit typically contain low levels of sulfur. For sulfur-containing feedstocks in refinery applications, a non-noble-metal catalyst was developed that is robust and sulfur-tolerant. Catalyst life based on commercial experience is expected to be 4 years or more provided the feedstocks meet design specifications. The C5 olefin streams can be used as alkylation process feed or as feedstock for the production of tertiary amyl methyl ether (TAME). Typically, the feedstock to a TAME Ethermax unit requires the reduction of dienes in the C5 olefin stream. In addition, 3-methyl-1-butene can be isomerized in the SHP unit to 2-methyl-1-butene and 2-methyl2-butene, which react to form TAME. This can increase the TAME yield by up to 8 wt %.
TABLE 8.2.1 Component 1-Butene, wt % 2-Butene, wt % 1,3-Butadiene, wt ppm Butyne, wt ppm Typical Modes of SHP Unit Operation Feed 14.6 23.4 4460 68 Mode 1 4.2 33.9 20 6 Mode 2 14.7 23.4 1 1

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SELECTIVE HYDROGENATION PROCESSES 8.28

HYDROTREATING

THE HLS SHP-CB PROCESS

The Hls SHP unit can also be modified to readily remove butadiene from feedstocks with high butadiene concentrations. For example, a crude C4 stream from a steam cracking unit can contain up to 60 wt % butadiene and can be readily processed by the Hls SHP-CB unit, where CB refers to concentrated butadiene. In the SHP-CB process, the use of multiple reactors together with a recycle stream reduces the butadiene concentration while controlling the exothermicity of the reaction. The SHP-CB process is operated at mild temperatures and moderate pressures. The product from the SHP-CB unit typically contains up to 10 wt ppm butadiene. The catalyst has a very high selectivity to monoolefins (99 percent) and is designed to give a high yield of 1-butene. The SHP-CB process can be used in the production of high-purity 1-butene. The product from the SHP-CB process can be sent to an MTBE Ethermax unit or UOP Indirect Alkylation (InAlk) Unit for the removal of isobutene. The MTBE or InAlk unit raffinate is then sent to the Hls Butene-1 Separation Process for recovery of high-purity 1-butene. In a typical scheme, n-butane and 2-butene are removed in an initial column, and high-purity 1-butene is recovered as the bottoms product in a second column. The fractionation of the different C4 components is difficult and requires a large number of stages. However, the use of UOP MD trays can provide significant cost savings in the fractionation section. The flow scheme for the production of 1-butene from a steam cracking unit feed is shown in Fig. 8.2.3.

COMMERCIAL EXPERIENCE
A total of nine KLP units have been licensed, and seven are in operation. Thirty-six SHP units and seven SHP-CB units have been licensed. Twenty-three of the SHP units are now on-stream, and three are under design or construction. Five of the SHP-CB units are now on-stream with an additional one under design or construction. Most of these units are designed for diene reduction to less than 5 wt ppm.

ECONOMICS AND OPERATING COSTS

The estimated erected cost of an SHP unit processing 200 kMTA (6373 BPD) FCC olefins with 1 percent dienes is $3.3 million U.S. (50 percent). This capital estimate is for an inside battery-limits unit erected in the U.S. Gulf Coast, fourth quarter 2002. The utility requirements for an SHP unit processing 200 kMTA (6373 BPD) are summarized in Table 8.2.2.

REFERENCES
1. J. P. Boitiaux, C. J. Cameron, J. Cosyns, F. Eschard, and P. Sarrazin, Selective Hydrogenation Catalysts and Processes, Erdoel Kohle, Erdgas, Petrochem. 47(4): 141145 (1994). 2. Gary Gildert and Richard Barchas, Selective Diolefin Hydrogenation, CDTECH, Pasadena, Tex., Ber.-Dtsch. Wiss. Ges. Erdoel, Erdgas Kohle Tagungsber, 9305: 5966 (1993).

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SELECTIVE HYDROGENATION PROCESSES

SELECTIVE HYDROGENATION PROCESSES

8.29 Butene-1 Column Light Ends & Isobutane

Butene-2 Column H2 Methanol

C4 Stream from Cracker

SHP-CB

Ethermax

MTBE

Butene-2 & Normal Butane

FIGURE 8.2.3 Production of 1-butene from crude C4s.

Butene-1

TABLE 8.2.2

Operating Utility Requirements 46 kWh 798 kg/h (798 kg/h) 51 m3/h 46 kWh 1760 lb/h (1760 lb/h) 223 gal/min

Power Medium-pressure steam (150 lb/in2 gage sat.) Condensate Cooling water

Note: Values in parentheses indicates net production.

3. H-M Allmann, Ch. Herlon, and P. Polanek, Selective Hydrogenations and Purifications in the Steamcracker Downstream Treatment. BASF AG, Ludwigshafen, Germany. Ber.-Dtsch. Wiss. Ges. Erdoel, Erdgas Kohle, Tagungsber 9305: 129 (1993). 4. F. Nierlich and F. Obenaus, Method for Selective Hydrogenation of Polyunsaturated Hydrocarbons in Olefin Mixtures. Huels A.-G., Marl, Fed. Rep. Ger. Erdoel Kohle, Erdgas, Petrochem. 39(2): 7378 (1986). 5. B. V. Vora and C. P. Luebke, Process Hydrogenates Unwanted Diolefins and Acetylenes, Oil and Gas Journal, Dec. 5, 1988, p. 5. 6. H. Abrevaya, B. V. Vora, and R. A. Lentz, Improved Butadiene Technology for Naphtha Cracking, UOP, Des Plaines, Ill., USA. Proceedings of Ethylene Producers Conference 5: 631636 (1996). 7. H. Abrevaya, B. V. Vora, E. H. Page, and M. J. Banach, Selective Hydrogenation of C4 Acetylenes by the KLP Process. UOP, Des Plaines, Ill., USA. (Proceedings of the DGMKConference: C4 ChemistryManufacture and Use of C4 Hydrocarbons, DGMK Tagungsber. 9705: 99106 (1997).

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SELECTIVE HYDROGENATION PROCESSES

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