Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 7.2

UOP UNICRACKING PROCESS FOR HYDROCRACKING

Donald Ackelson
UOP LLC Des Plaines, Illinois

INTRODUCTION
Hydrotreating and hydrocracking are among the oldest catalytic processes used in petroleum refining. They were originally employed in Germany in 1927 for converting lignite to gasoline and later used to convert petroleum residues to distillable fractions. The first commercial hydrorefining installation in the United States was at Standard Oil Compan y of Louisiana in Baton Rouge in the 1930s. Following World War II, growth in the use of hydrocracking was slow. The availability of Middle Eastern crude oils reduced the incentive to convert coal to liquid fuels, and new catalytic cracking processes proved more economical for converting heavy crude fractions to gasoline. In the 1950s, hydrodesulfurization and mild hydrogenation processes experienced a tremendous growth, mostly because large quantities of by-product hydrogen were made available from the catalytic reforming of low-octane naphthas to produce high-octane gasoline. The first modern hydrocracking operation was placed on-stream in 1959 by Standard Oil Company of California. The unit was small, producing only 1000 barrels per streamday (BPSD). As hydrocracking units were installed to complement existing fluid catalytic cracking (FCC) units, refiners quickly recognized that the hydrocracking process had the flexibility to produce varying ratios of gasoline and middle distillate. Thus, the stage w as set for rapid growth in U.S. hydrocracking capacity from about 3000 BPSD in 1961 to about 120,000 BPSD in just 5 years. Between 1966 and 1983, U.S. capacity grew eightfold, to about 980,000 BPSD. Outside the United States, early applications involved production of liquefied petroleum gas (LPG) by hydrocracking naphtha feedstocks. The excellent quality of distillate fuels produced when hydrocracking gas oils and other heavy feedstocks led to the choice of the hydrocracking process as a major conversion step in locations where diesel and jet fuels were in demand. Interest in high-quality distillate fuels produced by hydrocracking has increased dramatically worldwide. As of 2002, more than 4 million BPSD of hydrocracking capacity is either operating or is in design and construction worldwide.

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PROCESS APPLICATIONS
Hydrocracking is one of the most versatile of all petroleum refining processes. Any fraction from naphtha to nondistillables can be processed to produce almost any desired product with a molecular weight lower than that of the chargestock. At the same time that hydrocracking takes place, sulfur, nitrogen, and oxygen are almost completely removed, and olefins are saturated so that products are a mixture of essentially pure paraffins, naphthenes, and aromatics. Table 7.2.1 illustrates the wide range of applications of hydrocracking by listing typical chargestocks and the usual desired products. The first eight chargestocks are virgin fractions of petroleum crude and gas condensates. The last four are fractions produced from catalytic cracking and thermal cracking. All these streams are being hydrocracked commercially to produce one or more of the products listed. This flexibility gives the hydrocracking process a particularly important role as refineries attempt to meet the challenges of todays economic climate. The combined influences of low-quality feed sources, capital spending limitations, hydrogen limitations, environmental regulatory pressures, and intense competition have created a complex optimization problem for refiners. The hydrocracking process is uniquely suited, with proper optimization, to assist in solving these problems. UOP, with its broad background and research capabilities, has continued to develop both catalyst and process capabilities to meet the challenges.

PROCESS DESCRIPTION
The UOP* Unicracking* process is carried out at moderate temperatures and pressures over a fixed catalyst bed in which the fresh feed is cracked in a hydrogen atmosphere. Exact process conditions vary widely, depending on the feedstock properties and the products desired. However, pressures usually range between 35 and 219 kg/cm2 (500 and 3000 lb/in2 gage) and temperatures between 280 and 475C (536 and 887F).
*Trademark and/or service mark of UOP.

TABLE 7.2.1

Applications of the Unicracking Process Products Propane and butane (LPG) Naphtha Naphtha and/or jet fuel Naphtha, jet fuel, and/or distillates Naphtha Naphtha, jet fuel, distillates, lubricating oils Naphtha, jet fuel, distillates, lubricating oils Naphtha, distillates, vacuum gas oil, and low-sulfur residual fuel Naphtha Naphtha and/or distillates Naphtha Naphtha and/or distillates

Chargestock Naphtha Kerosene Straight-run diesel Atmospheric gas oil Natural gas condensates Vacuum gas oil Deasphalted oils and demetallized oils Atmospheric crude column bottoms Catalytically cracked light cycle oil Catalytically cracked heavy cycle oil Coker distillate Coker heavy gas oil

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Chemistry Hydrocracking chemistry is bifunctional catalytic chemistry involving acid-catalyzed isomerization and cracking reactions as well as metal-catalyzed hydrogenation reactions. The resulting products are lower in aromatics and contain naphthenes and highly branched paraffins due to the higher stability of the tertiary carbenium ion intermediate. For paraffins, the reaction network, shown in Fig. 7.2.1, is postulated to begin with a dehydrogenation step at a metal site forming an olefin intermediate, which is quickly protonated at an acid site to yield a carbenium ion. This is quickly followed by a series of isomerization reactions to the most stable tertiary carbenium ions and subsequent cracking to smaller paraffin, which evolves off the catalyst surface and smaller carbenium ion intermediate. The carbenium ion can then eliminate a proton to form an olefinic intermediate, which gets hydrogenated at a metal site or directly abstract a hydride ion from a feed component to form a paraffin and desorb from the surface. A typical hydrocracking reaction for a cycloparaffin (Fig. 7.2.2) is known as a paring reaction, in which methyl groups are rearranged and then selectively removed from the cycloparaffin without severely affecting the ring itself. Normally the main acyclic product is isobutane. The hydrocracking of multiple-ring naphthene, such as decalin, is more rapid than that of a corresponding paraffin. Naphthenes found in the product contain a ratio of methylcyclopentane to methylcyclohexane that is far in excess of thermodynamic equilibrium. Reactions during the hydrocracking of alkyl aromatics (Fig. 7.2.3) include isomerization, dealkylation, paring, and cyclization. In the case of alkylbenzenes, ring cleavage is almost absent, and methane formation is at a minimum.

FIGURE 7.2.1

Postulated paraffin-cracking mechanism.

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FIGURE 7.2.2

Postulated cracking mechanism for naphthenes.

FIGURE 7.2.3 Postulated aromatic-dealkylation mechanism. Isobutane is also formed following butyl carbenium ion isomerization, olefin formation, and hydrogenation.

Catalyst Hydrocracking catalysts combine acid and hydrogenation components in a variety of types and proportions to achieve the desired activity, yield structure, and product properties. Noble metals as well as combinations of certain base metals are employed to provide the hydrogenation function. Platinum and palladium are commonly used noble metals while the sulfided forms of molybdenum and tungsten promoted nickel or cobalt are the most

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UOP UNICRACKING PROCESS FOR HYDROCRACKING

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common base-metal hydrogenation agents. The cracking function is provided by one or a combination of zeolites and amorphous silica-aluminas selected to suit the desired operating and product objectives. A postulated network of reactions that occur in a typical hydrocracker processing a heavy petroleum fraction is shown in Fig. 7.2.4. The reactions of the multiring species should be noted. These species, generally coke precursors in nonhydrogenative cracking, can be effectively converted to useful fuel products in a hydrocracker because the aromatic rings can be first hydrogenated and then cracked. Amorphous silica-alumina was the first catalyst support material to be used extensively in hydrocracking service. When combined with base-metal hydrogenation promoters, these catalysts effectively converted vacuum gas oil (VGO) feedstocks to products with lower molecular weight. Over three decades of development, amorphous catalyst systems have been refined to improve their performance by adjustment of the type and level of the acidic support as well as the metal function. Catalysts such as UOPs DHC-2 and DHC-8 have a well-established performance history in this service, offering a range of activity and selectivity to match a wide range of refiners needs. Crystalline catalyst support materials, such as zeolites, have been used in hydrocracking catalysts by UOP since the mid-1960s. The combination of selective pore geometry and varying acidity has allowed the development of catalysts that convert a wide range of feedstocks to virtually any desired product slate. UOP now offers catalysts that will selectively produce LPG, naphtha, middle distillates, or lube base oils at high conversion activity using molecular-sieve catalyst support materials. The UOP zeolite materials used in hydrocracking service are often grouped according to their selectivity patterns. Base metal catalysts utilized for naphtha applications are HC-24, HC-34, and HC-170. Flexible base metal catalysts (naphtha, jet, diesel) include DHC-41, HC-43, HC-33, HC-26, and HC-29. The distillate catalysts, which offer a significantly enhanced activity over amorphous catalysts while maintaining the excellent middle-distillate selectivity, are HC-110, HC-115, DHC-32, and DHC-39. Noble metal catalysts are also available for both naphtha (HC-28) and jet/naphtha (HC-35) service. Unlike the amorphous-based catalysts, the zeolite-containing materials are usually more selective to lighter products and thus more suitable when flexibility in product choice is desired. In addition, zeolitic catalysts typically

FIGURE 7.2.4

Hydrocracking reactions.

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employ a hydroprocessing catalyst upstream, specifically designed to remove nitrogen and sulfur compounds from the feed prior to conversion. UOP catalysts such as HC-P, HC-R, HC-T, UF-210, and UF-220 are used for this service. These materials are specifically designed with high hydrogenation activity to effectively remove these compounds, ensuring a clean feed and optimal performance over the zeolitic-based catalyst. One important consideration for catalyst selection is regenerability. Hydrocracking catalysts typically operate for cycles of 2 years between regenerations but can be operated for longer cycles, depending on process conditions. When end-of-run conditions are reached, as dictated by either temperature or product performance, the catalyst is typically regenerated. Regeneration primarily involves combusting the coke off the catalyst in an oxygen environment to recover fresh catalyst surface area and activity. Regenerations can be performed either with plant equipment if it is properly designed or at a vendor regeneration facility. Both amorphous and zeolitic catalysts supplied by UOP are fully regenerable and recover almost full catalyst activity after carbon burn.

Hydrocracking Flow Schemes Single-Stage. The single-stage flow scheme involves full conversion through recycling of unconverted product and is the most widely used because of its efficient design resulting in minimum cost for a full-conversion operation. This scheme can employ a combination of hydrotreating and cracking catalysts or simply amorphous cracking catalysts depending on the final product required. Once-Through. Unlike the single-stage flow scheme, the once-through flow scheme is a partial conversion option that results in some yield of unconverted material. This material is highly saturated and free of feed contaminants but is similar in molecular weight to the feed. If a refinery has a use for this unconverted product, such as FCC feed or high-quality lube base oil, this flow scheme may be preferred. Two-Stage. In the two-stage flow scheme, feedstock is treated and partially converted once-through across a first reactor section. Products from this section are then separated by fractionation. The bottoms from the fractionation step are sent to a second reactor stage for complete conversion. This flow scheme is most widely used for large units where the conversion in the once-through first stage allows high feed rates without parallel reactor trains and the added expense of duplicate equipment. Separate-Hydrotreat. The separate-hydrotreat flow scheme is similar to single-stage, but is configured to send reactor effluent that has been stripped of hydrogen sulfide and ammonia to the cracking catalyst. This configuration allows the processing of feedstocks with very high contaminant levels or the use of contaminant-sensitive catalysts in the cracking reactor if dictated by product demands. The single-stage flow scheme is the most widely used hydrocracking flow scheme in commercial service. The flow scheme allows the complete conversion of a wide range of feedstocks and product recovery designed to maximize virtually any desired product. The design of this unit configuration has been optimized to reduce capital cost and improve operating performance. Greater than 95 percent on-stream efficiency is typical. Figure 7.2.5 illustrates a typical single-stage flow scheme. Feedstock, recycle oil, and recycle gas are exchanged against reactor effluent to recover process heat and are then sent through a final charge heater and into the reactor section. The reactor section contains catalysts that allow maximum production of the desired product slate. In virtually all hydrocracking systems, the combined reactions are highly exothermic and require cold hydrogen

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UOP UNICRACKING PROCESS FOR HYDROCRACKING

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FIGURE 7.2.5

Typical flow diagram of a single-stage Unicracking unit.

quench injection into the reactors to control reactor temperatures. This injection is accomplished at quench injection points with sophisticated reactor internals that both mix reactants and quench and redistribute the mixture. Proper mixing and redistribution are critical to ensure good temperature control in the reactor and good catalyst utilization through acceptable vapor or liquid distribution. In this typical configuration, reactor effluent is sent through exchange to a hot separator, where conversion products are flashed overhead and heavy unconverted products are taken as hot liquid bottoms. The use of a hot separator improves the energy efficiency of the process by allowing hot liquid to go to the fractionation train and prevents polynuclear aromatic (PNA) fouling of cold parts of the plant. The overhead from the hot separator goes to a cold separator, where recycle gas is separated from the product. The product is then sent to fractionation, and recycle gas is returned to the reactor via the recycle compressor. The fractionation train typically starts with a stripper column to remove hydrogen sulfide, which is in solution with the products. The removal ensures a relatively clean product in the main fractionator column, thus reducing column costs and metallurgy requirements. The stripper is followed by a main fractionating column with appropriate stages and sidedraws to remove the desired products. The bottoms from this main column is recycled back to the reactor section for complete feed conversion. To allow complete conversion without PNA fouling or excessive catalyst coking, UOP has developed several techniques to selectively remove PNAs from the recycle oil stream. Some PNA removal is critical for successful operation at complete conversion. In earlier designs, the unit was simply purged of PNAs by taking a bottoms drag stream. In newer units, PNAs may be selectively removed by either fractionation or adsorption. The result is an increased yield of valuable liquid product. HyCycle. HyCycle typically uses back-staged, series-flow cracking and hydrotreating reactors. The products and unconverted oil (UCO) from the hydrotreating reactor are separated in the high-pressure section, creating the recycle oil for the cracking reactor. Similar to separate-hydrotreat and two-stage configurations, the recycle oil is contaminant-free. Because of the efficient separation of UCO from products, the recycle oil rate can be increased above typical hydrocracking levels, allowing the cracking catalyst to operate at lower severity and produce higher yields. The HyCycle configuration provides the lowest operating and equipment cost for many operations.

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The HyCycle process uses a combination of several unique, patented design features to facilitate an economic full (99.5 percent) conversion operation at low (20 to 40 percent) conversion per pass. Another important feature of the process is reduced operating pressure. Relative to current practice, HyCycle Unicracking designs are typically 25 percent lower in design pressure. The key benefits of the process are lower hydrogen consumption and higher selectivity to heavier product. For example, up to 5 vol % more middle distillate yield with as much as a 15 percent shift toward diesel fuel can be achieved when compared to other full conversion maximum distillate designs. This shift in selectivity coupled with a more selective saturation of feed aromatics results in as much as a 20 percent reduction in process hydrogen requirement. In the process, cracked products and unconverted oil are separated in the HyCycle enhanced hot separator (EHS) at reactor pressure. The separated products are then hydrogenated in a posttreat reactor. This unique processing step maximizes the quality of the distillate product for a given design pressure. It also provides a more efficient means of recycling UCO to the cracking reactor, enabling a less severe (lower) per pass conversion that results in improved selectivity and yield. The hydrocracking catalyst zone configuration is referred to as back-staged because recycle oil is routed first to a hydrocracking catalyst zone and then to a hydrotreating catalyst zone. The benefits of back-staging include cleaner feedstock to the cracking catalyst and higher hydrogen partial pressure. The net result is higher catalyst activity per unit volume, hence a lower catalyst volume requirement. The reactors use a common series flow recycle gas loop to maintain the economic efficiency of a single-stage design. In addition, UOP low-temperature catalysts are used in the reactor(s) to enable higher combined feed rates without increasing reactor diameter or pressure drop. Figure 7.2.6 illustrates a typical HyCycle flow scheme. Products from Hydrocracking Hydrocracking units process lower-value, sulfurous feedstocks such as vacuum distillates and cracked stocks to produce higher-value fuels. There is tremendous flexibility, through choice of catalysts and unit configuration, to optimize product quality and yield structure. The hydrocracking process has a well-demonstrated versatility. This can be shown in the yield and product quality information shown in Table 7.2.2 for processing a Middle East VGO for maximum distillate and for maximum naphtha, the two extremes of hydrocracking operation. Improvements in Yield-Activity Relationships One of the difficult decisions refiners face when selecting hydrocracking technology is whether to sacrifice activity to gain yield, or sacrifice yield to gain activity. Many refiners in North America, for example, would like to increase C6 naphtha yield, but not at the cost of lower activity. They may also like a flexible catalyst for seasonal shifts in their product slate. Refiners in Europe and the Far East often ask for higher-activity distillate catalysts. To meet the needs of refiners around the world, UOP continues to develop catalysts that provide enhanced performance without sacrificing yield or activity. Figure 7.2.7 shows relative activity-selectivity curves for previous and current generations of UOP hydrocracking catalysts. Selectivity to diesel product is shown on the vertical axis, and the catalysts activity is shown on the horizontal axis. Each symbol on the curves represents a catalyst in the UOP portfolio. New generations of catalysts are currently being developed to improve these relationships.

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H2 HC Rx Feed Enhanced Hot Separator HT Rx HF PT Rx Amine Scrubber

Product To LPG Fractionator Recovery

Feed Gas

HPS CF

0.5% UCO
FIGURE 7.2.6 HyCycle Unicracking process schematic flow diagram.

TABLE 7.2.2

Typical Hydrocracker Yields* Distillate Naphtha 0.1 2.6 0.8 3.3 21.4 39.1 68.9

Yield: NH3, wt % H2S, wt % C2-, wt % C3, wt % C4, vol % Light naphtha, vol % Heavy naphtha, vol % Distillate, vol % Product properties: Jet fuel cut: Smoke point, mm Freeze point, C (F) Aromatics, vol % Diesel fuel cut: Cetane no. Total naphtha: P/N/A, vol Research octane no.

0.1 2.6 0.6 1.0 3.5 7.5 11.4 94.0

29 59 ( 74) 9 60

33/55/12 70

*Basis: Feedstock, Middle East VGO; density, 22.2 API; sulfur, 2.5 wt %. Note: P/N/A paraffins/naphthenes/aromatics; API degrees on American Petroleum Institute scale.

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Previous Generations Current Generation Distillates Selectivity Flexible Max Naphtha

Max Diesel

Distillates

Activity
FIGURE 7.2.7 formance. New generation Unicracking catalysts offer enhanced per-

INVESTMENT AND OPERATING EXPENSES

Capital investment and operating expenses for a hydrocracker are sensitive to

The processibility of the feedstock The desired product slate The desired product specifications

The desired product slate has a profound effect on the arrangement of equipment, as discussed in the previous section. If the feed has demetallized oil or is more difficult to process for some other reason, operating conditions can be more severe than in hydrocracking a VGO. This additional severity can be manifested in equipment, hydrogen consumption, utilities, and additional catalyst. In general, a jet fuel operation is more severe than an operation producing a full-range diesel product. Naphtha production requires a higher hydrogen consumption than either jet fuel or diesel production. Only typical examples can be given; not every case can be covered. The figures in the accompanying tables are for illustrations only; variation may be expected for specific cases. Typical capital investment guidelines are given in Table 7.2.3. Typical utility guidelines are given in Table 7.2.4.

AKNOWLEDGMENTS
I wish to acknowledge Dr. Suheil Abdo for his comments on the chemistry and catalyst sections of this chapter.

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TABLE 7.2.3

Hydrocracker Capital Investment* Distillate 25003500 Naphtha 20003000

Operation Estimated erected cost, $/BPSD CF

*As of January 1, 2002, based on combined-feed (CF) rate; includes 20 percent of material and labor as design engineering plus construction engineering cost; does not include hydrogen plant; BPSD barrels per stream-day.

TABLE 7.2.4

Typical Hydrocracker Utilities 200450 26 40120 0.110.22 (0.250.50) 0.08 (0.2)

metric tons per hour.

Power, kW Fired fuel, 106 Btu/h Cooling water, gal/min Medium-pressure steam, MT/h (klb/h) Condensate, MT/h (klb/h)
Note: Based on 1000-BPSD fresh feed; MT/h

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UOP UNICRACKING PROCESS FOR HYDROCRACKING

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