Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.4

UOP RCD UNIONFINING PROCESS

Daniel B. Gillis
UOP LLC Des Plaines, Illinois

INTRODUCTION
The UOP* RCD Unionfining* reduced-crude desulfurization process represents the merger of three of the worlds leaders in residual oil processing and catalyst technology. UOPs acquisition of the Unocal PTL Division in January 1995 resulted in the merging of UOP and Unocals catalyst technology, commercial know-how, and design experience to create a new, improved residual hydrotreating process. Prior to this acquisition in 1993, UOP entered into an alliance with Catalyst & Chemicals Ind. Co. Ltd. (CCIC) in Japan that enabled UOP to offer CCICs commercially proven portfolio of residual hydrotreating catalysts. In addition UOP has catalysts available from other leading catalyst manufacturers. The RCD Unionfining process provides desulfurization, denitrification, and demetallization of reduced crude, vacuum-tower bottoms, or deasphalted oil (DAO). Contaminant removal is accompanied by partial conversion of nondistillables. The process employs a fixed bed of catalyst, operates at moderately high pressure, consumes hydrogen, and is capable of greater than 90 percent removal of sulfur and metals. In addition to its role of providing lowsulfur fuel oil, the process is frequently used to improve feedstocks for downstream conversion units, such as cokers, fluid catalytic crackers (FCCs), and hydrocrackers.

MARKET DRIVERS FOR RCD UNIONFINING

The first commercial reduced-crude desulfurization unit, which came on-stream in 1967, was a licensed design from UOP. The residual hydrotreating units produced a low-sulfur fuel oil product that was in increasing demand as a result of the stringent laws relating to air pollution that were being enacted in the industrialized countries. Units were designed in the 1970s to produce fuel oil with a sulfur level as low as 0.3 wt %. The trend toward low-sulfur fuel oil has now extended around the world.
*Trademark and/or service mark of UOP.

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UOP RCD UNIONFINING PROCESS 8.44

HYDROTREATING

Other drivers have added to the need for the RCD Unionfining process. Fuel oil demand has been declining at a rate of about 0.2 percent per year since the 1980s, and this decline has been coupled with a growth of about 1.4 percent in the demand for refined products. As the demand for heavy fuel oil has fallen, the price differential between light and heavy crude oil has increased. This price differential has given the refiner an economic incentive to process heavy crude. However, heavy crude not only produces a disproportionate share of residual fuel, but also is usually high in sulfur content. Because heavy, high-sulfur crude is a growing portion of the worldwide crude oil reserves, refiners looking for future flexibility have an incentive to install substantial conversion and desulfurization capacity to produce the required product slate. In addition to providing low-sulfur fuel oil, the RCD Unionfining process provides excellent feedstock for downstream conversion processes producing more valuable transportation fuels.

CATALYST
Catalysts having special surface properties are required to provide the necessary activity and stability to cope with reduced-crude components. The cycle life of the catalyst used in the RCD Unionfining process is generally set by one of three mechanisms: Excessive buildup of impurities, such as scale or coke, that leads to unacceptable pressure drop in the reactor Coke formation from the decomposition and condensation of heavy asphaltic molecules Metal deposition in catalyst pores from the hydrocracking of organometallic compounds in the feed UOP provides a complete portfolio of catalysts to handle each of these three mechanisms (Table 8.4.1). Feed filtration for removing scale particulates is a standard part of the RCD Unionfining design. In most cases, this filtration satisfactorily prevents buildup of scale on the catalyst bed, and the resulting pressure drop does not limit cycle life. However, some feeds contain unfilterable components. Under these circumstances, the catalyst bed itself acts as a filter, and the impurities build up in the top section of catalyst to create unacceptable pressure drop. The CDS-NP series of catalyst helps prevent this problem by increasing the amount of void space in the top of the reactor for the impurities to collect. The CDS-NP catalysts are designed as a macaroni shape in 1/4-in and 1/6-in sizes. The macaroni shape maximizes the amount of void space and catalyst surface area available for deposition of the impurities. The catalysts are also loaded from the larger to smaller size. This kind of loading, which is called grading the catalyst bed, helps to maximize the void space available for deposition. Coke formation reduces catalyst effectiveness by decreasing the activity of the reactive surface and decreasing the catalyst-pore volume needed for metals accumulation. For a given catalyst and chargestock operating under steady-state conditions, the amount of coke on the catalyst is a function of temperature and pressure. Successful hydrodesulfurization of reduced crudes requires that temperatures and pressures be selected to limit coke formation. When coke formation is limited, ultimate catalyst life is determined by the rate of metals removal from organometallic compounds in reduced crude and by the catalyst-pore volume available for the accumulation of metals. The deposition rate of metals from organometallic compounds correlates with the level of desulfurization for a given catalyst. Thus, the rate of catalyst deactivation by metals

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TABLE 8.4.1 Catalyst name CDS-NP1 CDS-NP5

CCIC Catalyst Portfolio Application P relaxation and HDM

1/4 in shaped

Size and shape

CDS-NPS1 CDS-NPS5 CDS-DM1 CDS-DM5 CDS-R95 CDS-R25H CDS-R55

HDS

P relaxation and HDM HDM HDM HDM/HDS HDS HDS

1/6 in shaped

1/8, 1/12, 1/16, 1/22 in cylindrical or shaped

hydrodesulfurization; HDM

hydrodemetallization.

deposition increases with the increasing level of desulfurization. Metals deposition results from the conversion of sulfur-bearing asphaltenes. Conversion exposes catalyst pores to the portion of the feed that is highest in organometallics. The catalyst deactivation rate is also a function of feedstock properties. Heavier reduced crudes with high viscosities, molecular weights, and asphaltene contents tend to be more susceptible to coke formation. Hence, higher pressures and lower space velocities are required for processing these materials. Correlations developed on the basis of commercial data and pilot-plant evaluation of many different reduced crudes can predict the relationship between the hydrodesulfurization reaction rate and the deactivation rate and reduced-crude properties. The UOP-CCIC catalyst portfolio has been developed to maximize both the removal of sulfur, metals, and other impurities such as nitrogen and Conradson carbon and the life of the catalyst. The CDS-DM series catalysts are typically loaded downstream of the CDSNP catalysts and are designed for maximum metal-holding capacity. Although their metals-removal activity is high, they maximize the removal of the resin-phase metals and minimize the removal of asphaltene-phase metals. (For an explanation of the terms resin phase and asphaltene phase, see the following Process Chemistry section.) The removal of asphaltene-phase metals can lead to excessive formation of coke precursors, which ultimately reduce the life of downstream catalysts. The CDS-R9 series catalysts are typically located downstream of the CDS-DM catalysts. These transition catalysts have intermediate activity for demetallization and desulfurization and are used to gradually move from maximum demetallization to maximum desulfurization. Once again, the gradual transition helps to minimize the formation of coke precursors, which could lead to shortened catalyst life. The final catalysts are the CDS-R25/R55 series, which have maximum desulfurization activity. By the time the residual oil reaches this series of catalysts, the metals level is sufficiently low to prevent metals deactivation. In addition to this portfolio of conventional desulfurization and demetallization catalysts, several custom catalysts are available for the RCD Unionfining process. The R-HAC1 catalyst is a residual, mild-hydrocracking catalyst intended for use with lighter feedstocks. Although it has the same hydrodesulfurization activity as conventional HDS catalysts, it produces 3 to 4 vol % more diesel fuel without an increase in naphtha or gas yields. The CATX catalyst is designed as an FCC feed pretreatment catalyst. The FCC microactivity testing (MAT) of feeds processed over the CAT-X catalyst has shown an increase in the gasoline yield of as much as 5 percent. Typical catalyst loadings are shown in Fig. 8.4.1.

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UOP RCD UNIONFINING PROCESS 8.46

HYDROTREATING

= Nonplugging Type = HDM Type = HDS Type

FIGURE 8.4.1

Typical catalyst loading.

PROCESS CHEMISTRY
A residual (or resid) is a complex mixture of heavy petroleum compounds that are rich in aromatic structures, heavy paraffins, sulfur, nitrogen, and metals. An atmospheric residual (AR) is a material that has been produced in an atmospheric-pressure fractionation column as a bottoms product (ATB) when the boiling endpoint of the heaviest distilled product is at or near 343C (650F). The bottoms is then said to be a 343C (650F ) atmospheric residual. A vacuum residual (VR) is produced as bottoms product from a column running under a vacuum when the boiling endpoint of the heaviest distilled product is at or near 566C (1050F). The bottoms is then said to be a 566C (1050F ) vacuum residual. Residual components can be characterized in terms of their solubility: Saturates. Fully soluble in pentane; this fraction contains all the saturates. Aromatics. Soluble in pentane and separated by chromatography; this fraction contains neutral aromatics. Resins. Soluble in pentane and absorb on clay; this fraction contains polar aromatics, acids, and bases. Asphaltenes. Those that are insoluble in pentane (pentane insolubles) and those that are insoluble in heptane (heptane insolubles); the weight percent of pentane insolubles is always greater than the weight percent of heptane insolubles. Typically, the conversion reaction path in the RCD Unionfining process is from asphaltenes to resins, resins to aromatics, and aromatics to saturates. With the exception of the lightest fractions of crude oil, impurities can be found throughout the petroleum boiling range. Impurity concentrations of each fraction increase with the boiling point of the fraction. Examples of this situation for sulfur and nitrogen are shown in Figs. 8.4.2 and 8.4.3. Of all the components in the residual, the asphaltene components are the most difficult to work with. Asphaltene molecules are large and are rich in sulfur, nitrogen, metals (Fe, Ni, V), and polynuclear aromatic compounds. These components are primarily the ones that deactivate the catalyst through metals contamination or coke production. Characterization of some typical atmospheric residuals along with their respective asphal-

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FIGURE 8.4.2

Sulfur distribution.

FIGURE 8.4.3

Nitrogen distribution in Hondo California crude.

tene components is shown in Table 8.4.2. An example of an asphaltene structure can be seen in Fig. 8.4.4. Typically, the impurities are buried deep inside the asphaltene molecule, and so severe operating conditions are required to remove them.

PROCESS DESCRIPTION
Operating Variables For a specific feedstock and catalyst package, the degree of demetallization, desulfurization, and conversion increases with the increasing severity of the RCD Unionfining operation. The operating variables are pressure, recycle-gas rate, space velocity, and temperature.

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UOP RCD UNIONFINING PROCESS 8.48 TABLE 8.4.2

HYDROTREATING

AR Characterization Crude source Arabian Heavy Hondo 5.9 372 13.9 7.7 1130 Maya 4.4 500 25.2 6.4 1570

AR properties: Sulfur, wt % NI V, wt ppm Asphaltenes, wt % Asphaltene properties: Sulfur, wt % Ni V, wt ppm

4.29 108 12.6 6.5 498

FIGURE 8.4.4

Asphaltene structure.

Pressure. Increasing hydrogen partial pressure decreases the catalyst deactivation rate at constant reactor temperature because the formation of carbonaceous deposits, which deactivate the catalyst, is thereby retarded. The increased pressure also increases the activity for desulfurization, demetallization, and denitrification. Increased hydrogen partial pressure can be obtained by increasing total pressure or by increasing the hydrogen purity of the makeup gas, which together with a recycle-gas scrubber to remove H2S maximizes hydrogen partial pressure. Recycle-Gas Rate. Increasing the recycle-gas rate increases the hydrogen/ hydrocarbon ratio in the reactor. This increased ratio acts in much the same manner as increased hydrogen partial pressure. Space Velocity. Increasing the space velocity (higher feed rate for a given amount of catalyst) requires a higher reactor temperature to maintain the same impurity removal level and results in an increase in the deactivation rate. Temperature. Increasing temperature increases the degree of impurity removal at a constant feed rate. operating at an increased temperature level increases the catalyst deactivation rate. as the catalyst operating cycle proceeds, reactor temperature is usually increased because of the disappearance of active catalyst sites.

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Impact of Feedstock Quality and Processing Objectives The ease of processing a feedstock depends on the nature of the asphaltenic molecule and the distribution of contaminants throughout the resin and asphaltene fractions. Relative processing severity is dependent on feedstock type and processing objectives (Fig. 8.4.5). Consequently, the process operates over a large range of operating conditions: 1500 to 3000 lb/in2 and 0.10 to 1.0 LHSV. Feedstocks with high contaminants, such as vacuum residues, typically have higher pressures and lower space velocities.

Process Flow A simplified flow diagram of the UOP RCD Unionfining process is presented in Fig. 8.4.6. The filtered liquid feed is combined with makeup hydrogen and recycled separator offgas and sent first to a feed-effluent exchanger and then to a direct-fired heater. In this flow scheme, the direct-fired heater is shown as a two-phase heater, but the alternative of separate feed and gas heaters is also an option. The mixed-phase heater effluent is charged to a guard bed and then to the reactor or reactors. As indicated earlier, the guard bed is loaded with a graded bed of catalyst to guard against unacceptable pressure drop, but this catalyst also performs some impurities removal. Removal of the remaining impurity occurs in the reactor. The RCD Unionfining reactors use a simple downflow design, which precludes problems of catalyst carryover and consequent plugging and erosion of downstream equipment. Because this reactor system has three phases, uniform flow distribution is crucial. UOP provides special reactor internals to ensure proper flow distribution. The reactor-effluent stream flows to a hot separator to allow a rough separation of heavy liquid products, recycle gas, and lighter liquid products. The hot separator overhead is cooled and separated again to produce cold separator liquid and recycle gas, which is scrubbed to remove H2S before being recycled. A portion of the scrubbed recycle gas is sent to membrane separation to reject light components, mainly methane, that are formed in the reactor. If these components are not removed, they could adversely affect the hydrogen partial pressure in the reactor. Hot separator liquid is fed to a hot flash drum, where the overhead is cooled and mixed with cold separator liquid, and the mixture is charged to the cold flash drum. Bottoms from both the hot and cold flash drums are charged to the units fractionation system, which can be set up to either yield low-sulfur fuel oil or match feed specifications for downstream processing.

Vacuum Resid AR

Catalyst Volume Pressure

Atmospheric Resid DAO VGO Desulfurization

FIGURE 8.4.5

DAO
Required processing severity versus feedstock type.

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UOP RCD UNIONFINING PROCESS 8.50

HYDROTREATING

Fixed Bed Reactors Residue Feed Feed Filters

Hot Separator

H2 Makeup H2 Recovery Purge H2S Scrubber Cold Separator To Fuel Gas Hot Flash Fractionator Gas Naphtha Distillate Cold Flash Hydrotreated Residue

FIGURE 8.4.6 RCD Unionfining process.

Process Applications As trends toward heavier crudes and lower fuel oil demand have become evident, UOP has devoted increased attention to bottom-of-the-barrel processing. As a result, several flow schemes that offer a variety of advantages have been developed. The most common of these flow schemes is shown in Fig. 8.4.7. Atmospheric residual oil is directly hydrotreated to provide FCC feed. Hydrotreating allows a high percentage of the crude to be catalytically cracked to gasoline while maintaining reasonable FCC catalyst consumption rates and regenerator SOx emissions. Hydrotreating can also help refiners meet some of the newly emerging gasoline sulfur specifications in most parts of the world. For upgrading residual oils high in metals, the best processing route may be a combination of solvent extraction (UOP/FWUSA solvent deasphalting process) and the RCD Unionfining process. The SDA process separates vacuum residual oil with a high metal content into a deasphalted oil (DAO) of relatively low metal content and a pitch of high metal content. The pitch has several uses, including fuel oil blending, solid-fuel production, and feed to a partial-oxidation unit for hydrogen production. If the metal and Conradson carbon content of the DAO are sufficiently low, it may be used directly as an FCC or hydrocracker feed component. In some cases, however, hydrotreating the DAO prior to cracking is desirable, as shown in Fig. 8.4.8. This combination of processes shows better economics than either process alone. The arrangement provides an extremely flexible processing route, because a change in feedstock can be compensated for by adjusting the ratio of DAO to pitch in the SDA unit to maintain DAO quality. In some cases, the treated material can be blended with virgin vacuum gas oil (VGO) and fed directly to the conversion unit. When the RCD Unionfining process is used to pretreat coker feed (Fig 8.4.9), it reduces the yield of coke and increases its quality and produces a higher-quality cracking feedstock. Of course, these examples are just a few of the bottom-of-the-barrel upgrading flow schemes involving the RCD Unionfining process. The correct selection of flow scheme is typically specific to a given refiners needs and crude type.

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Crude

Crude Fractionation

RCD Unionfining
FIGURE 8.4.7 Maximum gasoline production.

RCC

Reduced Crude

Vacuum Fractionation

RCD Unionfining

To FCC or Hydrocracker

UOP/FWSDA Pitch to Fuel Oil Visbreaking, Solid Fuel, or Partial Oxidation

FIGURE 8.4.8 Maximum flexibility flow scheme.

Crude

Crude Fractionation

To FCC or Hydrocracker

RCD Unionfining

Vacuum Fractionation

Coke Feed
FIGURE 8.4.9 High-quality coke production.

OPERATING DATA
The yield and product properties for processing a blended Middle Eastern reduced crude in an RCD Unionfining unit are shown in Table 8.4.3. Utilities required to operate a 132.5m3/h [20,000 barrels per stream-day (BPSD)] RCD Unionfining unit are shown in Table 8.4.4. The estimated erected cost for this unit is $70 million.

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UOP RCD UNIONFINING PROCESS 8.52 TABLE 8.4.3

HYDROTREATING

Yields and Product Properties of a Middle East Blend Reduced Crude Yields on reduced crude Wt % Specific Vol % gravity Sulfur, wt % 4.1 Nitrogen, vol % 0.31 Viscosity, cSt at 50C 2259 V N, ppm 141

Charge: Raw oil Chem. H2 consump. Products: NH3 H2S C2 C3 C4 C5154C 154360C 360C Total

100.00 100.00 12.1 1.29 (140 m3/m3) 0.19 3.91 0.67 0.36 0.36 1.10 14.70 80.00 101.29 1.50 0.720 16.70 0.868 84.20 0.935 102.40

0.004 0.02 0.47

0.004 0.02 0.17

23 151

18

TABLE 8.4.4 Typical Utilities Required for an RCD Unionfining Unit* Per barrel Hydrogen Catalyst Power HP steam Cooling water 750 SCF 0.1 lb 5 kWh 11 lb 22 gal Per cubic meter 127 nm3 0.29 kg 31.5 kWh 31.4 kg 0.5 m3

COMMERCIAL INSTALLATIONS
The first commercial direct reduced-crude desulfurization unit was a UOP unit that went on-stream in 1967 at the Chiba, Japan, refinery of Idemitsu Kosan. The first commercial direct vacuum-resid conversion unit was a UOP unit that went on-stream in 1972 at the Natref, South Africa, refinery. A total of 27 RCD Unionfining units have been licensed. As of early 2002, more than 143,000 m3/h (900,000 BPSD) of RCD Unionfining capacity has been licensed. These units process a variety of feeds, including DMOs and vacuum resids and atmospheric resids. Applications for this process include conventional desulfurization, downstream conversion unit pretreatment, and resid nondistillable conversion.

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