Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.3

UOP UNIONFINING TECHNOLOGY

Peter Kokayeff
UOP LLC Des Plaines, Illinois

INTRODUCTION
Hydrotreating is one of the most mature technologies found in the refinery, rivaling the history and longevity of the thermal process. In 1952, UOP and Union Oil Co. of California began licensing hydrotreating under the name of the Unifining process. The partnerships and the development of this technology have gone through a series of changes over the years, and in 1995 the acquisition of the Unocal Process Technology and Licensing group by UOP resulted in the merger of two premier hydroprocessing companies and the combination of their expertise under the UOP* Unionfining* banner. Generally speaking, the hydrotreating process removes objectionable materials from petroleum distillates by selectively reacting these materials with hydrogen in a catalyst bed at elevated temperature. These objectionable materials include sulfur, nitrogen, olefins, and aromatics. Lighter materials such as naphtha are generally treated for subsequent processing in catalytic reforming units, and the heavier distillates, ranging from jet fuel to heavy vacuum gas oils, are treated to meet strict product-quality specifications or for use as feedstocks elsewhere in the refinery. Many of the product-quality specifications are driven by environmental regulations that are becoming more stringent each year. This push toward more environmentally friendly products is resulting in the addition of hydroprocessing units in refineries throughout the world.

PROCESS CHEMISTRY
The chemistry behind the hydrotreating process can be divided into a number of reaction categories: (hydro)desulfurization, (hydro)denitrification, saturation of olefins, and saturation of aromatics. For each of these reactions, hydrogen is used to improve the quality of the petroleum fraction.
*Trademark and/or service mark of UOP.

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Desulfurization Desulfurization is by far the most common of the hydrotreating reactions. Sulfur-containing hydrocarbons come in a number of forms, and the ability to remove sulfur from the different types of hydrocarbons varies from one type to the next. The degree to which sulfur can be removed from the hydrocarbon varies from near-complete desulfurization for light straight-run naphthas to 50 to 70 percent for heavier residual materials. Figure 8.3.1 lists several sulfur-containing compounds in order of the difficulty in removing the sulfur. The reaction of thiophenol, which is at the top of the list in Fig. 8.3.1, proceeds quite rapidly; the reaction is shown schematically in Fig. 8.3.2. Multiring thiophene-type sulfurs are more difficult to treat because the ring structure, which is attached to the sulfur on two sides, must be broken. Figure 8.3.3 is a schematic representation of the reaction for the desulfurization of dibenzothiophene. In each case, the desulfurization reaction results in the production of hydrogen sulfide (H2S) in the reactor section of the plant. To complete the desulfurization reaction, the H2S must be removed in downstream fractionation. Denitrification The nitrogen compounds that occur naturally in crude oils and that would normally be found in the feed to a hydrotreater can be classified into two categories: basic nitrogen,

FIGURE 8.3.1

Relative desulfurization reactivities.

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FIGURE 8.3.2

Desulfurization of thiophenol.

FIGURE 8.3.3

Desulfurization of dibenzothiophene.

which is generally associated with a six-member ring, and neutral nitrogen, which is generally associated with a five-member ring. Examples of these two types of nitrogen are shown in Fig. 8.3.4. The complexity of the nitrogen compounds makes denitrification more difficult than desulfurization. The denitrification reaction first proceeds through a step that saturates the aromatic ring. This saturation is an equilibrium reaction and normally sets the rate at which the denitrification reaction can occur. Figure 8.3.5 is a schematic representation of a denitrification reaction. The combination of aromatic saturation followed by denitrification results in an increase in the amount of hydrogen required compared to desulfurization. This

FIGURE 8.3.4

Types of nitrogen compounds.

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FIGURE 8.3.5 Denitrification of quinoline.

increased hydrogen consumption also translates to an increase in the amount of heat generated. The denitrification reaction results in the generation of ammonia (NH3). To complete the processing, this NH3 must be removed in downstream fractionation. Olefin Saturation Although desulfurization is the most common of the reactions, olefin saturation also proceeds quite rapidly. As shown in Fig. 8.3.6, hydrogen is added to an olefin, and the corresponding saturated compound is the product. This reaction is quite fast and highly exothermic. If a significant quantity of olefins is present in the feed, the resulting heat release must be accounted for in the unit design. The ease with which this reaction takes place allows for operation at lower temperatures than the other hydrotreating reactions discussed in this section.

Aromatic Saturation Aromatic saturation occurs according to the same principles as olefin saturation in that hydrogen is added to saturate the double bonds in the aromatic or benzene ring. The aromatic or benzene ring is a six-carbon atom ring that contains three double bonds (Fig. 8.3.7). Because this ring structure is quite prominent in many of the materials found in the

FIGURE 8.3.6

Typical olefin saturation reactions.

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FIGURE 8.3.7

Benzene ring.

refinery, the symbol for this benzene ring is simplified and indicated as a hexagon with a circle inside. Figure 8.3.8 schematically shows three typical aromatic saturation reactions. The S inside the ring represents a six-member carbon ring that has had all the double bonds saturated. Because these aromatic-saturation reactions are highly exothermic, maintaining a proper temperature profile in the reactor is important. As the catalyst deactivates, the temperatures are raised to maintain conversion until end-of-run (EOR) conditions are approached. In the case of aromatic saturation, EOR occurs when the equilibrium no longer favors aromatic saturation.

Metals Removal In addition to the previously mentioned typical hydroprocessing functions, the Unionfining unit may be designed to remove low levels of metals from the feed. The metals to be removed include nickel and vanadium, which are native to the crude oil, as well

FIGURE 8.3.8

Typical aromatic saturation reactions.

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as silicon and lead-containing materials that are added elsewhere in the refinery. These metals are poisons to downstream processing units and can pose environmental problems if they are contained in a fuel product that will eventually combust. In the past, refiners would operate their hydrotreating unit until the hydrotreating catalyst had no more capacity to absorb metals. In a hydrotreating unit, the reactor is loaded with a catalyst that is designed specifically to have a high capacity for metals removal if the feed metals are anticipated to be high.

CATALYST
The primary function of the catalyst used in the hydrotreating reaction is to change the rate of reactions. The suitability of a catalyst depends on a variety of factors related to the feed quality and processing objectives. The catalysts used in the UOP Unionfining processes are typically a high-surface-area base loaded with highly dispersed active metals. For hydrodesulfurization operations, the preferred catalyst has been a cobalt molybdenum (Co/Mo) catalyst as it has a higher activity for desulfurization than nickel molybdenum (Ni/Mo) catalysts when the product sulfur level is high, that is, . 200 wt ppm S, meeting present-day environmental regulations. With much more stringent regulations slated to take effect within the next few years, a nickel molybdenum catalyst may be the optimal choice (see discussion of distillate unionfining for ULSD). Typical compositions of Co/Mo and Ni/Mo catalysts are shown in Table 8.3.1.

TABLE 8.3.1 Typical Composition of Unionfining Catalysts Species CoO or NiO MoO3 Al2O3 Range, wt % 16 625 Balance

In denitrification operations, a catalyst with a different hydrogen function is required to allow operation at normal temperatures. In these instances, the nickel molybdenum catalyst is more common. These catalysts are also good desulfurization catalysts; however, their hydrogen consumption could be higher because of their better denitrification activity. Either of these catalysts provides adequate activity for the saturation of olefins. As previously mentioned, these reactions are fast and occur at temperatures lower than those required for desulfurization or denitrification. For the saturation of aromatics, the selection of the proper catalyst is quite dependent on the processing objectives. In many cases, a nickel molybdenum catalyst provides the required level of aromatic saturation. In cases where the feed aromatics content is high or the product aromatics specification is low, UOP might suggest a catalyst that has some level of noble metal (such as platinum or palladium) to be used after the nickel molybdenum catalyst. The metals-removal catalysts are designed specifically for the purpose of removing metals from the feed so that they do not affect the hydrotreating capability of the hydroprocessing catalyst. These catalysts typically have a different shape or pore structure or both

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than the normal hydrotreating catalyst and are often designed to have some reduced level of desulfurization or denitrification activity.

PROCESS FLOW
The actual flow scheme of the UOP Unionfining process varies, depending on the application. Figure 8.3.9 provides a generic look at the flow scheme of a UOP Unionfining unit. The feed is exchanged with the reactor effluent, mixed with recycle hydrogen, and then heated to reaction temperature in a fired heater. The combined feed then flows through the reactor, which contains the catalyst that will accelerate the reaction. The reactor effluent is cooled in exchange with the feed and then in a series of coolers before being separated in a vapor-liquid separator. The vapor portion is recompressed, combined with fresh hydrogen, and returned to the reactor feed. The liquid portion is fed to a fractionator, where it is stripped of light ends, H2S, and NH3.

UNIONFINING APPLICATIONS
Generally speaking, the most common way to categorize hydrotreating applications is by feed type. This section provides general information on a limited number of Unionfining applications.

Naphtha Unionfining The main use of the hydrotreating process in naphtha applications is in the preparation of feedstocks for the naphtha reforming unit. The reforming process requires low levels of sulFresh Feed Recycle Gas Compressor

Reactor

Heater

Wash Water Light Ends Separator Stripper Steam Sour Water Makeup Compressor

Hydrogen Makeup

Desulfurized Product

FIGURE 8.3.9

Typical Unionfining process flow.

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fur, nitrogen, and metals in the feed. The Unionfining process reduces the sulfur and nitrogen to less than 0.5 wt ppm and the metals to nondetectable levels. For olefinic feeds, the Unionfining process is also used to stabilize the naphtha by completely saturating the olefins. A comparison of the typical processing conditions of the various hydroprocessing operations indicates that naphtha feeds are typically the easiest to hydrotreat. Table 8.3.2 provides a list of typical operating conditions for the applications discussed in this section. Distillate Unionfining A distillate Unionfining process is typically used to improve the quality of kerosene, jet fuel, and diesel oils. While the usual objective is to effect a desired degree of desulfurization, process conditions, and catalyst choice can be adjusted to achieve a desired improvement in other properties such as cetane number (smoke point for jet fuels), stability, color, odor, or aromatics content of the product. Distillate Unionfining for ULSD (Ultralow-Sulfur Diesel) Recent environmental regulations will require a quantum leap in the reduction of sulfur in diesel fuels. While present regulations mandate a sulfur content of 500 wt ppm (U.S.) and 350 wt ppm (Europe), recently enacted legislation requires that the sulfur level be reduced to 15 wt ppm (by 2006 in the United States) and 10 wt ppm (by 2007 in Europe) before the end of the decade. To meet these more stringent regulations, new, more active catalysts are required as well as more severe operating conditions. To achieve these very low levels of sulfur, the catalyst must be able to desulfurize the most difficult sulfur speciessterically hindered dibenzothiophenes. These compounds contain alkyl groups in the 4- and 6-positions, thus greatly restricting access to the sulfur atom. An illustration of the difficulty of desulfurizing these types of compounds is given in Fig. 8.3.10. Since the difficult sulfur species are thiophenic, lets consider the relative reaction rates shown in Fig. 8.3.10, starting with thiophene which is assigned a desulfurization rate of 100. As the thiophene molecule becomes more complex and bulky with the addition of an aromatic ring, as in benzothiophene, the desulfurization rate drops to 60. With the addition of another aromatic ring, dibenzothiophene, the rate of desulfurization decreases by an order of magnitude to 5. Addition of substituents to the rings at positions far removed from the sulfur atom, as in 2,8-dimenthyldibenzothiophene, do not affect the rate of desulfurization. On the other hand, addition of substituents at positions adjacent to the sulfur atom, as in 4,6-dimenthyldibenzothiophene, greatly reduces the rate of desulfurization to a relative rate of 0.5. the difficulty in desulfurizing 4,6-dimethyldibenzothiophene (and comTABLE 8.3.2 Typical Hydrotreating Operating Conditions Naphtha 1.05.0 50 (300) 14 (200) 290 (555) Middle distillate 1.04.0 135 (800) 38 (400) 330 (625) Light gas oil* 0.71.5 255 (1500) 49 (700) 355 (670) Heavy gas oil 0.752.0 337 (2000) 55 (800) 355 (670)
stan-

Operating conditions LHSV H2 /HC ratio, N m3/mm3 (SCF/B) H2 partial pressure, kg/cm2 (psia) SOR temperature, C (F)

Note: LHSV liquid hourly space velocity, N standard temperature and pressure, SCFB dard cubic feet per barrel. *Conditions to desulfurize light gas oil to ULSD specifications ( 10 wt ppm sulfur).

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Thiophene S Benzothiophene S Dibenzothiophene 2,8 Dimethyldibenzothiophene S 4,6 Dimethyldibenzothiophene CH3

FIGURE 8.3.10 Relative reaction rates.

100 60 5 S CH3 CH3 5 0.5 S CH3

pounds of a similar structure with alkyl substituents adjacent to the sulfur atom) is due to the steric hindrance these substituents present to access of the sulfur atom to the active site of the catalyst. For the production of the ULSD, it is these most difficult sulfur species that must undergo desulfurization. In addition to the difficulty of desulfurizing the sterically hindered dibenzothiophenes, the impact of a number of poisons for the desulfurization reaction must be considered. These include nitrogen and oxygen compounds. While the toxic effect of these poisons may have been neglected in the past, it must be taken into account for a successful design of a unit for ULSD production. Based on fundamental mechanistic and kinetic studies, present theory suggests that in order to desulfurize these molecules, one of the aromatic rings must first undergo saturation. Since Ni/Mo catalysts have better saturation activity than Co/Mo catalysts, the former are preferred for deep desulfurization of distillates to ULSD specifications. The requirement to effect such a deep level of desulfurization will necessitate the application of much more severe process conditions for distillate Unionfining than were necessary in the past (Table 8.3.2). Vacuum Gas Oil Unionfining A vacuum gas oil (VGO) Unionfining process is typically designed to either upgrade the feed quality for further processing or improve the VGO quality so that it can be used as an environmentally friendly fuel oil. Typically, further processing of the VGO occurs in a fluid catalytic cracking (FCC) unit or in a hydrocracking unit. As can be seen in Table 8.3.2, the conditions required to hydrotreat a VGO stream are more severe than those required to hydrotreat feedstocks with lower molecular weight. As a result, some low-level (10 to 30 percent) conversion can take place in a VGO Unionfining unit. This conversion requires that the product fractionation be designed to recover lighter products for use elsewhere in the refinery or for blending with the refinery product streams. RCD Unionfining Process The RCD Unionfining process for hydrotreating residual hydrocarbons is not discussed in this chapter; however, the principles involved are the same, but the processing conditions are more severe (Table 8.3.2).

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INVESTMENT
The investment associated with the installation of a hydrotreating unit depends on the feed characteristics and the product specifications. Generally speaking, as the feed gets heavier or the individual product specifications are reduced, the processing requirements are increased. These more severe processing conditions can result in more pieces of equipment, larger equipment, and higher operating pressure, all of which increase the cost of the unit. The required capital investment for a hydrotreating unit can vary from $500 to $2000 U.S. per barrel per stream-day of capacity.

UOP HYDROPROCESSING EXPERIENCE

The Unionfining process is really a broad family of fixed-bed hydrotreating processes. Naphtha, distillate, VGO, and RCD. Unionfining units are in operation throughout the world. UOPs Unionfining experience is broken down by application in Fig. 8.3.11. More than 500 commercial units have been designed, and these units process literally hundreds of different feed streams.

FIGURE 8.3.11

Unionfining experience.

BIBLIOGRAPHY
Ackelson, Donald B., David A. Lindsay, Robert E. Miller, and Milan Skripek: HydrotreatingHydrocracking, Annual Conf. on International Refining and Petrochemicals, Singapore, May 910, 1994. Baron, Ken, Robert E. Milner, Alice Tang, and Laurie Palmer: Hydrotreating of Light Cycle Oil, Annual Meeting of National Petroleum Refiners Association, New Orleans, Mar. 2224, 1992. Bjorklund, Bradford, L., Timothy L. Heckie, Neil D. Howard, David A. Lindsay, and David J. Piasecki: The Lower It Goes the Tougher It Gets (The Practical Implications of Producing UltraLow Sulfur Diesel, Annual Meeting of National Petroleum Refiners Association, San Antonio, March 2629, 2000. Maddox, Ronnie, Tom Karlnes, and David A. Lindsay: Integrated Solutions for Optimized ULSD Economics, Annual Meeting of National Petroleum Refiners Association, San Antonio, Mar. 2425, 2003.

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Nguyen, Tuan A., and Milan Skripek: Reducing Sulfur in FCC Gasoline via Hydrotreating, AIChE Spring National Meeting, Apr. 1721, 1994. Nguyen, Tuan, and Milan Skripek: VGO Unionfining: Technical Case Studies, Hydrocarbon Technology International, Sterling Publications Ltd., London, 1993.

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