Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.7

CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

Avinash Gupta
Chevron Lummus Global Bloomfield, New Jersey

INTRODUCTION
Ongoing trends in the petroleum refining industry have resulted in the need to upgrade bottom-of-the-barrel heavy oils that otherwise are difficult to transport and market due to their high viscosity and high levels of contaminants, such as sulfur, metals, asphaltenes, carbon residues, and solid particles. Petroleum refiners find it necessary to process heavier crudes that require deep residual conversions to produce clean, high-quality finished products. The LC-Fining residual hydroconversion process was developed to specifically target hydrocracking the worlds most difficult, heavy, lower-value hydrocarbon streams (petroleum residuals, heavy oils from tar sands, shale oils, solvent-refined coal extracts, etc.) at conversion levels of 80 percent and higher. Increasing demand for light and middle distillates, as well as changing environmental regulations and specifications for fuel oil production, has further increased the need for more efficient residuum upgrading processes. The LC-Fining process, when coupled with an integrated, fixed-bed, wide-cut hydrotreater/hydrocracker, produces high-quality finished products without significant quantities of undesirable by-products. Earlier heavy vacuum residual technologies (carbon rejection or hydrogen addition type) were generally limited to distillate yields of 40 to 60 percent. The remaining unconverted bottoms were used as coke, low-BTU gas, or residual fuel oil. A major process route for coping with these challenges is residue hydrocracking. This process is characterized by both thermal cracking and hydrogenation reactions whereby the heavy, hydrogen-deficient components in the feed are converted to lighter products. The LC-Fining process is a commercially proven hydrocracking process for the upgrading of residues.
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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.68
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Residual upgrading process requirements should include the ability to (1) handle high heats of reaction without wasting reactor volume, (2) handle extraneous material without plugging, (3) provide uniform distribution of reactants and efficient contacting, and (4) operate over extended periods without shutdown. The nature of the LC-Fining process makes it ideally suited for the conversion of residues to lighter, more valuable products. The process can be tailored for the feedstocks, the degree of conversion, and the product qualities required, especially the production of high-quality residual fuel oil with low sulfur content and good pipeline stability, or high-quality synthetic crude oils. The LC-Fining process is based on technology initially developed and commercially demonstrated by Cities Service, and subsequently improved and refined by ABB Lummus Global, BP (formerly Amoco Oil Company), and ChevronTexaco Corp. (formerly Chevron). With this process, heavy oil feedsincluding gas oils, petroleum atmospheric and vacuum residue, coal liquids, asphalt, bitumen from tar sands, and shale oilare hydrogenated and converted to a wide spectrum of lighter, more valuable products such as naphtha, light and middle distillates, and atmospheric and vacuum gas oils. Residual products can be used as fuel oil, synthetic crude, or feedstock for a coker, visbreaker, solvent deasphalter, or residual catalytic cracker. Operating conditions and catalyst type and activity can be varied to achieve the desired conversion, Conradson carbon reduction (CCR), desulfurization, and demetallization of residual oil feeds.

DEVELOPMENT AND COMMERCIAL HISTORY

From 1957 to 1975, Cities Service Research and Development Company participated with Hydrocarbon Research Institute (HRI) to pilot-test and develop an ebullated bed hydroconversion process (H-Oil). During this period, research and development programs were continually carried out in several pilot units. Based on the pilot tests, the first commercial unit was designed and operated at Lake Charles, Louisiana, in 1963. In 1975, ABB Lummus Global (Lummus) joined together with Cities Service to license, market, design, and generally improve upon the technology from Cities Service. Pilot-plant facilities for this technology, called LC-Fining, were built in New Jersey. Lummus carried out comprehensive process pilot-plant studies and mechanical design developments and offered initial operation and process simulation services. The first license was sold to Amoco Oil Company in 1981. Amoco operated the commercial plant in Texas City, conducted extensive pilot-plant and catalyst development work, and eventually became a joint licensor with Lummus in 1984. The Amoco unit started up quickly and performed well right from the beginning: All design targets were met or exceeded. To maximize profits, throughout its operation, the Amoco unit processed the optimum-priced crudes available based on the characteristics of the residual bottoms to be processed in the LC-Fining unit (i.e., high sulfur/high metals content feedstocks, including blends with over 40 percent Mexican Maya). Amoco installed its own LC-Fining pilot-plant facilities in 1980. Lummus was given access to much of the information from these pilot units as well as that from Syncrude Canadas pilot unit, which operated from 1988 to 1998. Over many years, Lummus developed a large pilot-plant and commercial units database on various residual feeds from different geographic locations with a wide range of contaminant levels (metals, sulfur, nitrogen, CCR, asphaltenes, etc.). Some of these residual feeds included the worlds most difficult, very heavy, lower-value hydrocarbon streams. Lummuss pilot units were used to conduct many programs for design data development for various potential clients and the U.S. government. At one time, there were three

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

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ebullated bed pilot plants operating continuously in addition to mini-stirred autoclave test facilities. Many of the Middle Eastern, Mexican, Venezuelan, western Canadian, southeastern Asia, Russian, and U.S. reduced crudes and vacuum bottoms, solvent-refined coal extracts, heavy oils from tar sands, and shale oils were processed in Lummuss pilot-plant facilities. When the H-Oil process was developed, the initial goal was to process Athabasca bitumen for Cities Service Athabasca (now Syncrude Canada). Many of the pilot programs conducted from 1957 to 1972 were devoted to Athabasca bitumen. In the 1970s and 1980s Lummus also conducted numerous pilot runs on bitumen feeds for Syncrude. In the early 1990s, an extensive pilot program was performed for Alberta Oil Sands Technology Research Administration (AOSTRA) in order to demonstrate Lummuss high conversion technology (LC-Fining) with Athabasca bitumen and other Alberta heavy crudes. During this work, the integrated hydrotreater was closely studied and piloted at conditions that could be applied commercially. In 1990, a 70-day pilot-plant run was conducted on Arabian Heavy vacuum residue in Lummuss research facilities to support AGIP Petroli Raffineria di Milazzos (RAM) commercial LC-Fining unit design. In this run, a series of test programs were conducted at varying operating conditions and using various feed diluents and cutter stocks. The primary objective of the run was to establish the reactor operating conditions and proper feed diluent blends that would permit the maximum level of conversion to be attained, consistent with meeting RAMs low-sulfur fuel oil requirements. The commercial unit, commissioned in September 1998, has been running with an on-stream time in excess of 96 percent while producing 1 wt % sulfur stable fuel oil. In 1995, Russian vacuum residual supplied by Slovnaft for its refinery in Bratislava, Slovakia, was processed in Lummuss pilot-plant facility at conversion levels ranging from 60 to 88 vol %. For operations at higher conversion levels, an aromatic solvent (heavy cycle oil) was used with the vacuum residual, using high-HDS and low-sediment activity catalysts. This catalyst was superior to the standard LC-Fining catalyst tested in earlier runs in terms of sediment control and hydrodesulfurization (HDS) and CCR activity. The objective of this pilot run was to establish the reaction yields and product qualities to be used in the design and guarantees for Slovnafts commercial LC-Fining unit. The Slovnaft plant is similar to the RAM unit and has been successfully operating since 2000. In 2000, Lummus and Chevron joined forces to jointly develop and market the residual upgrading technologies of both companiesincluding the LC-Fining processunder a single entity, Chevron Lummus Global LLC (CLG). In 1999 and 2000, two LC-Fining pilot plant runs were conducted at CLGs facilities to support Shell Canadas and Petro-Canadas commercial LC-Fining units design efforts. During the Shell Canada run, a close-coupled, online, integrated, wide cut distillate, fixed-bed hydrotreater was also tested. In addition, off-line hydrotreating tests were performed to replicate the inhibition effects of H2S and NH3 expected in commercial operation. Under a joint cooperative agreement, CLG and AGIP Petroli conducted several pilotplant runs in the LC-Fining pilot-plant facility at AGIPs research center related to process optimization/ development and catalyst screening programs for RAM, Shell Canada, and Petro-Canada. The long-term goals of this joint effort are to extend the database, further enhance the correlations and models, test new process designs (e.g., interstage separator/stripper, optimize quantity and interstage injection location of aromatic diluents), and continue to screen and evaluate new residual conversion catalysts. CLG has built and is building several small pilot units at Chevrons research facilities in Richmond, California to support its residual upgrading technologies: ARDS, VRDS, OCR, upflow reactor (UFR), and LC-Fining.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.70
HYDROTREATING

PROCESS CHEMISTRY
Residual hydrocracking is accomplished at relatively high temperatures and high pressures in the presence of hydrogen and a residual conversion catalyst to hydrogenate the products and prevent polymerization of the free radicals as cracking reactions proceed. The catalyst consists of a combination of metals that promote hydrogenation (e.g., cobalt and molybdenum, or nickel and molybdenum) deposited on an alumina base. The two most important reactions that take place in residual hydrocracking are thermal cracking to lighter products and catalytic removal of feed contaminants. These reactions generally require operating temperatures between 750 and 850F, hydrogen partial pressures from 1100 to 2200 lb/in2, and space velocities ranging from 0.1 to 0.8 (vol oil/h)/vol of reactor. Hydrocarbons present in the residual are generally classified as oils, resins, and asphaltenes. Typical residual may contain about 20 percent oils, 65 percent resins, and 15 percent asphaltenes. The asphaltenes are the high-molecular-weight material in the residual that typically contains a large concentration of sulfur, nitrogen, metals, Conradson carbon, and highly condensed polynuclear aromatics. Nitrogen removal is generally much more difficult than sulfur removal. Some nitrogen compounds in the cracking reactions are merely converted to lower-boiling-range nitrogen compounds rather than being converted to NH3. The highest concentration of metals (V and Ni) resides in the asphaltene fraction with some in the resin fraction. The oil fraction tends to be nearly free of metals. Metals are removed as metal sulfides. Unlike sulfur and nitrogen, which are converted and escape as H2S and NH3, the vanadium and nickel removed are absorbed on the catalyst. These metals are known to plug the catalyst pores, and this pore blockage results in catalyst deactivation. The conversion of Rams carbon is economically important if LC-Fining vacuum bottoms are fed to a downstream coking unit. A lower-Rams-carbon-content residual product to the coking unit means less coke make and thus a higher yield of liquid fractions that can subsequently be converted to transportation fuels. Another option to limit the coke make in the downstream coking unit is to maximize the pitch conversion at the LC-Fining residual hydrocracker.

Residual Conversion Limits There are many factors that affect the sediment formation rate and consequently the reactor operability and residual conversion limits, including

Residual asphaltene content CCR reactivity Thermal severity (conversion) Catalyst type and activity Hydrogen partial pressure Type and quantity of diluents Residual resin content Reactor temperature

Of these, the first six have the greatest influence. Many pilot-plant tests showed that sediment formation is directly proportional to the asphaltene content of the feed and inversely proportional to the CCR reactivity.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

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Coke Precursor/Organic Sediment Formation The nature and origin of the coke precursors are often not precisely known. However, a mechanism of sediment (i.e., coke precursor) formation in processes that involve thermal cracking in addition to hydrocracking and hydrogenation, such as the LC-Fining process, has been generally postulated as described by the following reaction chemistry. Thermal crackingformation of free radicals R R R* R*

Free radicals react to form olefins or asphaltenes: R CH2 CH2* R CH R* R RR CH2 H*

Termination or recapping of free radicals by hydrogenation R* H* R H

At elevated temperatures, thermal cracking reactions generate free-radical species due to the rupture of carbon-carbon bonds. The free radicals may react with hydrogen in the presence of the catalyst to form stable products. This reaction predominates in the LC-Fining process where high hydrogen partial pressures are always maintained. If proper conditions are not maintained, the free radicals may also combine with other free radicals to form higher-molecular-weight free radicals. This chain reaction can continue until very high-molecular-weight, insoluble species (coke precursors/sediments) are produced. As the temperature is increased to obtain higher conversions, the rate of generation of free radicals, and consequently coke precursors, can increase, creating phase separation and potential instability in the reactor if it is allowed to exceed the solubility limit.

Means of Controlling Coke Precursors/Organic Sediments Control of coke precursors (organic sediments) can be accomplished in three ways: (1) Their formation is minimized or eliminated by using extremely high hydrogen partial pressures or very active catalyst; (2) the coke precursors are maintained in solution by adding aromatic diluents; and/or (3) the coke precursors are removed from the system. The catalyst used in the LC-Fining process has an excellent ability to control the formation of these coke precursors, and aromatic diluents have been used successfully. The continuous, physical removal of coke precursors (via filtration, centrifugation, etc.) from the reactor loop can be accomplished by bottoms recycle and removal of the coke precursors from the recycle stream, an approach pilot-tested and patented by Lummus for high conversion LC-Fining.

Catalyst Deactivation The rate at which a catalyst deactivates during residual oil hydrocracking is a complex function of many parameters that can be categorized into three distinct classes. The first consists of the physical and chemical properties of the residual feedstock to be processed. The second is concerned with the nature of the catalyst itself. The third is the effect of the

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.72
HYDROTREATING

operating conditions used to obtain the desired levels of conversion and desulfurization (temperature, space velocity, hydrogen partial pressure, etc.). The most significant causes of catalyst deactivation are metals and carbon laydown. Concurrent with the desulfurization of residuals is a demetallization reaction. Residual cracking products have nickel and vanadium contents markedly lower than those in the feed to the unit. The metals accumulate on the catalyst, causing deactivation. It has been proposed that the organometallics simply block the outer physical surface of the catalyst. Carbon laydown on catalyst is influenced by feedstock characteristics and conversion severity. Carbon accumulation is high in all operating scenarios, ranging from slightly under 10 wt % for low-temperature hydrodesulfurization of atmospheric residuum to over 40 wt % for high conversion of vacuum bottoms. Residual hydrocracking is apparently diffusion-controlled. It has been found that 1/32 in catalyst performs better than 1/16 in catalyst.

LC-FINING REACTOR
Following is a schematic of an ebullated bed LC-Fining reactor (Fig. 8.7.1). Fresh feed and hydrogen enter the reactor at the bottom and pass up through a catalyst bed where hydrodesulfurization and other cracking and hydrogenation reactions occur. A portion of the product at the top of the reactor is recycled by means of an internally mounted recycle pump. This provides the flow necessary to keep the catalyst bed in a state of motion somewhat expanded over its settled level (i.e., ebullated). The catalyst level is monitored and controlled by radioactive density detectors, where the source is contained inside the reactor and the detectors are mounted outside. Temperature is monitored by internal couples and skin couples. The performance of the ebullated bed is continuously monitored and controlled with the density detectors and temperature measurements that verify proper distribution of gas and liquid throughout the catalyst bed. Temperature deviations outside the normal expected ranges that might suggest maldistribution will cause the distributed control system (DCS) to activate alarms or initiate automatic shutdown on the heaters, hydrogen feed, and/or reactor section, as required. Catalyst is added and withdrawn while the reactor is in operation. The reactors can be staged in series, where the product from the first reactor passes to a second reactor and, if necessary, to a third reactor. After the final reactor, the product goes to a highpressure/high-temperature separator.

LC-FINING PROCESS FLOW SCHEMATICS

Process Description Following is a simplified process flow diagram of an LC-Fining unit with a close-coupled, integrated, fixed-bed hydrotreater/hydrocracker (Fig. 8.7.2). Oil feed and hydrogen are heated separately, combined, and then passed into the hydrocracking reactor in an upflow fashion through an ebullated bed of catalyst. Under the effects of time, temperature, and hydrogen pressure, and aided by the catalysts, the feed oil is cracked and hydrogenated to produce lighter, higher-quality products. A portion of the liquid product from the large pan at the top of the reactor is recycled through the central downcomer by means of a pump mounted in the bottom head of the reactor. This flow gives the needed velocity for bed expansion and aids in maintaining near-isothermal reactor temperature.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

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Effluent Thermowell Nozzle

Catalyst Addition Line Density Detector Radiation Source Well Density Detectors

Normal Bed Level

Skin TC's Catalyst Withdrawal Line

Feed Recycle Pump

FIGURE 8.7.1

LC-Fining reactor.

The hydrocracking reactions are exothermic, resulting in a temperature rise from inlet to outlet depending upon the reaction operating severity. However, because of the mixing effect of the internal recycle liquid, the bed operates essentially isothermally. Catalyst is added and withdrawn batchwise to maintain an equilibrium catalyst activity without the need for unit shutdown. Reactor products flow to the high-pressure/high-temperature separator. Vapor effluent from the separator is let down in pressure before heat exchange, removal of condensates, and purification. Handling the recycle gas at low pressure offers considerable savings in investment over the conventional high-pressure recycle gas purification system. After stripping, the recycle liquid is pumped through the coke precursor removal step (a physical means of separation such as centrifugation) where very small quantities of insoluble heavy hydrocarbons or carbonaceous solids are removed. The clean liquid recycle then passes to the suction drum of the feed pump. Net product from the top of the recycle stripper goes to fractionation; net heavy oil product is directed from the stripper bottoms pump discharge to vacuum fractionation. The LC-Fining reactor effluent vapor, along with distillate recovered from the heavy oil stripper overhead, any virgin atmospheric gas oil recovered in the prefractionator upstream of the LC-Fining unit, and vacuum gas oil recovered in the LC-Fining vacuum fractionator, is all charged to a wide-cut, close-coupled, integrated, fixed-bed hydrotreater/hydrocracker located immediately downstream from the last ebullated bed LC-Fining reactor. The inlet temperature to the first bed is controlled by adjusting the amount of heat extracted from the LC-Fining reactor vapor stream, and the temperature of the distillate liquid is controlled by a combination of hydrogen and liquid quench. The effluent from the hydrotreating reactors is separated into a vapor and heavy distillate liquid stream, with the

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Expanded Bed HP/HT Separator Reactor LP/HT Separator PSA Wash Water M.U. H2 H2S Removal Fuel Gas LP/LT Separator

Fixed Bed Reactor

LP/HT HP/HT Separator Separator

STM BFW

H2S Amine

H2 Heater

Feed

Oil Heater Distillate Recycle Surge Drum LP/MT Separator

Distillate Products Fractionation LP/LT Separator Compression

Bottoms Recycle (Optional)

Recycle Stripper

Coke Precursor Removal

ST

Recycle Heater Residue Vacuum Fractionation

CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

Coke Precursors

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FIGURE 8.7.2

Process flow sketchLC-fining unit with integrated distillate hydrotreating (LP recycle gas system).

CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

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liquid stream routed to the hydrotreated distillate fractionator. The vapor stream is aminetreated, purified through a pressure swing absorption (PSA) or membrane unit, and recompressed and recirculated as treat gas to the LC-Fining reactors. The high-conversion ( 80 percent) LC-Fining process differs from the basic process in that bottoms recycle is practiced. The recycle liquid is let down in pressure and passes to the recycle stripper where it is fractionated to the proper boiling range for return to the reactor. In this way, the concentration of bottoms in the reactor, and therefore the reaction products slate, can be controlled.

LC-FINING TECHNOLOGY ADVANTAGES

Several advances in the LC-Fining residual hydroconversion technology have significantly reduced the capital investment and have further extended the conversion limits and processing limitations. These include

H2 purification systems Low treat gas rates Integrated hydrotreating/hydrocracking Interreactor separator/stripper Modified recycle pan Vacuum bottoms recycle Reactor bottom head distributor Improved reactor distributor design

H2 Purification Systems One of the key areas of process optimization resulted in the H2 purification system. In early designs (Amoco), a lean oil system was used to purify the recycle gas, and the maximum purity achievable was 82 percent. In 1984, Lummus developed and patented a low-pressure H2 purification system, which has been utilized in all commercial operating units since. With low-pressure H2 purification, the gas exiting the last reactor is immediately let down and cooled at low pressure and then purified in a PSA unit. This permits high hydrogen treat gas purities, generally exceeding 97 vol %. As a result, the treat gas circulation rates were reduced by 50 to 60 percent and the reaction system design pressure by 10 percent, while still satisfying the hydrogen partial pressure requirements. This change, in conjunction with replacing 12 high-pressure equipment services (including high-pressure exchangers and drums; high-pressure lean oil and amine absorbers; and lean oil, amine, and wash water pumps) with low-pressure equipment, significantly reduced the LC-Fining unit investment cost. The only drawback with this low-pressure H2 purification scheme (i.e., using a PSA system) is that the recycle gas had to be recompressed from low pressure back to reactor operating pressure, requiring an increase of 25 to 30 percent in the overall power consumption. In 1998, the use of membranes was evaluated for purification of the recycle gas, and similar treat gas purities were achieved with membranes as with a PSA system. Membranes allow the same reduced reaction system pressure and lower treat gas circulation rates as with a PSA unit, but with the added benefit that the purified recycle gas is available at higher pressures. Consequently, the recycle gas can be recompressed in a sin-

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.76
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gle stage of compression versus the two or three stages of compression required with a PSA system, resulting in a 20 percent reduction in the overall unit power consumption. In addition, based on current high-pressure equipment pricing, the unit investment is slightly less with membranes than with a PSA unit.

Low Treat Gas Rates By using high-purity recycle gas, it is possible to achieve the desired hydrogen partial pressure with much lower hydrogen treat gas rates. The low gas rates have two primary benefits: They greatly reduce unit investment associated with the heating, cooling, purification, and recompression of the recycle hydrogen; and they significantly reduce the gas superficial velocity and therefore the gas holdup in the reactor. This provides for greater liquid residence time per unit reactor volume, thereby reducing the reactor volume required to achieve the desired thermal conversion and catalytic contaminants removal. Conversely, when designing to a maximum allowable superficial gas velocity within a specified reactor diameter constraint, it is possible to substantially increase the LC-Fining unit capacity. Reduced gas rates enhance overall reactor operation since internal liquid recirculation is increased as a result of the reduced gas superficial velocity and holdup. This results in better back-mixing of liquid and catalyst within the reactor, thereby minimizing incidences of catalyst bed slumping and channeling and flow maldistribution. The use of low treat gas rates is seen in all commercially operating LC-Fining units, which operate with a total hydrogen/chemical hydrogen ratio of 2.5:3.

Integrated Fixed-Bed Hydrotreater/Hydrocracker Several recent designs incorporated a close-coupled, integrated, fixed-bed hydrotreater/ hydrocracker immediately downstream of the LC-Fining reactors. In this design, the vapor stream from the LC-Fining reactors, the distillate recovered from the heavy oil stripper overhead, and the straight-run atmospheric and vacuum gas oils are fed to a wide-cut, fixed-bed hydrotreater/hydrocracker operating at essentially the same pressure level as the LC-Fining reactors. Excess hydrogen contained in the LC-Fining reactor effluent vapor is used to hydrotreat the distillate fractions. Additional hydrogen, equivalent only to the chemical hydrogen consumed in the fixed-bed reactor, is introduced as quench to the second and third catalyst beds. If necessary, the remaining portion of the reaction heat is dissipated by injecting liquid quench recycled from the separator downstream of the hydrotreater/hydrocracker. LC-Fining reactor effluent vapor is first contacted with VGO in a wash tower in order to remove any potential residual entrainment and entrainment of catalyst fines into the fixed-bed reactor. To maintain the desired HDS/HDN fixed-bed catalyst activity over the run length, a certain percentage of demetallization catalyst is included on the top of the first bed to remove metals and CCR contained in the hydrotreated feed fraction. Residual carryover is mitigated by providing additional surge upstream and by having spare (i.e., redundant) upstream separator and wash tower level control systems. By incorporating the fixed-bed hydrotreater within the LC-Fining reaction system, the HP system service count is reduced from approximately 14 pieces (for a stand-alone hydrotreater) to only 6. In addition, since excess hydrogen in the LC-Fining reactor effluent vapor is used to hydrotreat the straight-run and LC-Fining distillate fractions, the need for additional recycle gas compression is eliminated. As a result, the investment is significantly reduced compared to that for a stand-alone hydrotreater/hydrocracker.

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Interreactor Separator/Stripper Recently proposed process design configurations incorporate the use of an interreactor separator/stripper, which permits higher liquid capacities to be achieved for a given reactor cross section. Gas superficial velocities through the downstream reactors are reduced by separating the vapor between reaction stages and routing the vapor to the final reactor effluent separator. This design provides for parallel flow of gas to each reaction stage while maintaining the benefits of series flow liquid operations. In a conventionally designed unit, the effluent vapor from the upstream reactor is combined with additional treat/quench gas, and all the vapor is directed to the downstream reactors. It is possible to process much higher feed throughputs to the LC-Fining unit for a given reactor cross-sectional area. The reduction in stripped feed to the second-stage reactor and the associated increase in residual concentration enable reactor volume to be reduced for a given capacity and conversion, while the higher final-stage hydrogen partial pressure can be utilized to reduce either the catalyst addition rate or the reactor operating/design pressure. More important, the reduction in the paraffinic naphtha and light distillate fractions in the more highly converted thirdstage liquid reduces the sediment formation for a given residual conversion. The residual conversion limits can be further extended due to this change in liquid composition.

Liquid Recycle Pan A modified, two-stage, liquid recycle pan design, which increased conversion in the reactor and minimized upsets associated with the recycle pump bed expansion system, was put in operation at Amoco in 1986 and at Syncrude in 1988. The design operated with a more quiescent zone in and above the pan than the original version, minimizing the entrainment of gas bubbles into the recycle fluid, which in turn minimized gas holdup in the reactor. With this modification at Syncrudes LC-Fining unit, the conversion increased approximately 4 percent for the same reactor operating conditions. Subsequently, Amoco and Syncrude, with Lummuss participation, developed a new pan design aimed at permitting operation at still higher capacities and treat gas rates. Following the installation of this new pan at Syncrude in 1996, Syncrude has been able to charge 58,000 BPSD of 650F A-tar (unit originally designed for 40,000 BPSD), at similar reactor gas inlet superficial velocities, while achieving a 975F conversion of 57 to 58 vol %. Thus, the installation of this new pan increased conversion an additional 2 to 3 vol %.

Bottom Head Feed Distributor Based on cold flow modeling work done by Amoco in 1985/1986, a bottom head feed distributor was added to the LC-Fining reactors. It provides for better mixing of the feed oil, gas, and recycle oil while providing for better distribution of oil and gas to the cap and riser assembly.

Reactor Distributor Design The primary reactor grid distributor is a bubble cap type with slotted risers for distribution of vapor and liquid to each cap. Each riser contains a seat and ball to prevent back-migration of catalyst below the grid into the reactor bottom head, should the recycle pump stop. The seat contains a small V notch to permit oil to be drained from the reactor.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.78
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Amoco performed substantial cold flow modeling of the distributor grid that led to the installation of catalyst slides. This was found to reduce instances of localized catalyst settling near the wall, maintaining a cleaner reactor environment and increasing the run length between turnarounds. Alternate grid modifications are being considered, such as using larger risers around the reactor perimeter and/or varying the riser slot heights to either increase the flow of both gas and liquid, or, preferentially, increase the flow of gas, at the reactor wall.

Vacuum Bottoms Recycle Operation without Coke Precursor Removal Vacuum bottoms recycle (VBR) operations have been extensively pilot-tested, and VBR was found beneficial to

Increase residual conversion Minimize hydrogen consumption Maximize yield of vacuum gas oil Minimize light ends (C1-C3, gas) make Maximize unit capacity for a given level of conversion and reactor volume

The most significant advantage of VBR operation is the increase in residual conversion at the same operating severity. With VBR, the residual concentration increases within the reactors, thereby increasing the conversion rate. VBR does have some drawbacks. The operating company may prefer the higher yield of lighter distillates realized without recycle. Recycle is a form of back-mixing and can result in higher impurities in the product. Recycle of vacuum bottoms at higher temperatures is ineffective for control of sediment, as the sediment formation can rise rapidly, creating potential difficulties for maintaining proper catalyst bed ebullition.

COMMERCIAL OPERATIONS
Residue hydroconversion units that utilize the ebullated bed LC-Fining technology are summarized in Table 8.7.1. Shell Canada is scheduled to start up in 2003 and Petro-Canada around 2005.

PROCESS FLEXIBILITY
The LC-Fining unit has great inherent flexibility to meet variations in feed quality/throughput, product quality, and reaction operating severities (temperature, space velocity, conversion, etc.). This flexibility is a direct result of the ebullated catalyst bed reactor system. In an ebullated bed unit, if the metals or sulfur content of the feed increases, the product quality is maintained by increasing catalyst consumption. Conversely, the catalyst consumption is reduced if the feed quality improves. BP has utilized this flexibility to process heavy sour vacuum bottoms from a blend of different crudes, including Maya and Bachequero. At the same time, BP has increased conversion of vacuum bottoms to distillate to 75 to 80 percent typically, at full feed rate, and up to 92 percent at reduced feed rates. The original design was 60 percent at full feed rate.

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TABLE 8.7.1 Syncrude Athabasca bitumen 40,000 Produce synthetic crude Produce diesel oil and FCC feed Produce maximum FCC feed Produce synthetic crude oil (SCO) and stable heavy oil 77 Produce moderate-sulfur stable heavy product 75 Produce delayed coker feed 25,000 23,000 80,000 50,000 Obtain maximum conversion to distillates Vacuum residual Vacuum residual A-Tar, vacuum residual A-Tar, vacuum residual AGIP Slovnaft Shell Canada Petro-Canada

LC-Fining Commercial Units

Unit

BP

Feed

Vacuum residual

Capacity, BPSD

75,000

Process goal

Produce distillates

Residual conversion, vol % 65 Produce a reduced CCR feed to fluid coker Produce high-quality, low-sulfur No. 6 fuel oil Produce low-sulfur No. 6 fuel oil 6580 65

7580

LC-Fining bottoms utilization

Produce low-sulfur fuel oil

Produce feed for delayed coker Low Low Low Low Low

CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

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H2 purification system pressure

High

CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.80
HYDROTREATING

The worlds first ebullated bed residual upgrader operated by Cities Service Oil Company utilized this flexibility to process atmospheric bottoms, FCC heavy cycle oil, propane deasphalter bottoms, and vacuum bottoms. The Syncrude unit was originally designed to process 500F Athabasca bitumen containing 55 wt % 975F vacuum residual. More recently, they installed a vacuum prefractionation system and are now processing a blend of atmospheric and vacuum bottoms containing 75 wt % 975F vacuum residual. Sufficient operating flexibility is also normally provided in the design to enable the unit to operate in the future with VBR, which provides for future options to increase either conversion or unit throughput.

TYPICAL RANGE OF OPERATING PARAMETERS

Reactor temperature Reactor pressure Conversion, vol % 525C (975F ) Hydrogen partial pressure Hydrogen consumption Desulfurization Demetallization CCR reduction 400450C (750840F) 100200 atm (15003000 lb/in2 gage) 4092 percent 70170 atm (11002500 lb/in2 absolute) 120340 N m3/m3 (7002000 SCF B) 6095 percent 7098 percent 4075 percent

WIDE RANGE OF FEEDSTOCKS

A wide range of heavy oils have been processed in LC-Fining units. For example, the BP unit handles many of the poorest-quality vacuum residual in the world, including Mexican, Venezuelan, and Middle Eastern. Feed typically is under 5 API and has more than 4 wt % sulfur and more than 400 ppm metals. Table 8.7.2 shows the major crudes processed by BP at Texas City to produce LC-Fining feedstock from 1984 to 1992. Table 8.7.3 shows the BP unit operating results.

YIELDS AND PRODUCT QUALITY

LC-Fining unit product yields for processing Arabian heavy vacuum bottoms to conversion levels of 40, 65, and 80 percent are listed in Table 8.7.4. All these conversions can be achieved in the same LC-Fining unit, illustrating the great flexibility of the process. The yield structure and product properties are estimated from generalized correlations that were derived from extensive pilot-plant and commercial data. Typical product properties for a 65 vol % conversion case are shown in Table 8.7.5.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION

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TABLE 8.7.2 Major Crudes Processed by BP at Texas City to Produce LCFining Feedstock, 1984 to 1992 Maya Hondo Heavy Bachequero Lloydminster Alaskan North Slope West Texas C Khafji Jobo Menemota Gulf of Suez Mix Isthmus Alberta Light Pilon Laguana BCF-17 Tia Juana Pesado Djeno Arab Medium Arab Heavy Coban Cold Lake Peace River Yemen Olmeca Basrah Light Basrah Heavy Qua Iboe Merey Leona Kuwait Kirkuk

Feedstock: Blend of Maya (over 40 percent), Venezuelan, Middle Eastern, domestic including ANS, and other vacuum bottoms.

TABLE 8.7.3

BP Unit Operating Results

Performance Maximum* Conversion, % Sulfur removal, % Carbon residue, % Days on-stream to turnaround Percentage Maya bottoms 80 83 65 1095 43

*Items in this column were at different times.

TABLE 8.7.4

Typical LC-Fining Unit Product Yields Arabian heavy vacuum bottoms catalytic cracker HCO

Crude source:

Conversion Level 40 Feed Gravity, API Sulfur, wt % Nitrogen, wt % Ni/V, wt ppm CCR, wt % Product yields, vol % C4 C5329F 329698F 6981022F 1022F Total 1022F sulfur, wt % 1.07 5.50 19.18 30.77 48.00 104.52 1.2 942 1.02 5.20 19.10 31.10 48.00 104.32 1.6 870 40 5.4 4.7 0.35 189 20.8 1.45 7.60 31.50 36.96 28.00 105.51 1.6 1239 2.21 12.00 42.80 34.41 16.00 107.41 2.3 1590 65 80

Hydrogen consumption, SCF B fresh feed

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS 8.82 TABLE 8.7.5
HYDROTREATING

LC-Fining Unit Product Properties Arabian heavy 65 vol % conversion

Boiling range, F Wt % on feed Vol % on feed Gravity, API Sulfur, wt % Nitrogen, wt % Aniline point, F Cetane index Conradson carbon, wt % Metals: Vanadium, wt ppm Nickel, wt ppm Viscosity, CST @ 74F 210F 300F 350F C7, Asphaltenes, wt %

C5329 5.27 7.60 61.2 0.01 0.02

329698 26.50 31.50 31.2 0.11 0.08 122 41

6981022 33.71 36.95 19.0 0.53 0.19 163

1022 28.25 28.00 4.6 1.6 0.45

26.3 48 26 4.6 1.2 7.8 3.1

70 30 9.3

CATALYSTS
A series of catalysts are available for use in LC-Fining units. The first-generation catalysts in commercial use had adequate HDM/HDS activity with acceptable sediment levels. These were less expensive than more recently developed, enhanced contaminant removal/sediment control catalysts. New-generation catalysts are needed to produce low-sulfur fuel oils (from vacuum bottoms) of 1 wt % sulfur or less with minimum sediment levels ( 0.15 wt %) for pipeline stability. The other requirement of a good LC-Fining catalyst is to maintain improved reactor operability/stability at high-temperature/high-residual conversions. The residual hydroprocessing catalysts are small (1/32 to 1/8 in), extruded, cylindrical pellets made from an aluminum base. The pellets are impregnated with active metals (Co, Ni, Mo, W, and other proprietary materials) that have good hydrogenation, demetallation, desulfurization, and sediment control activity. Catalyst manufacturing processes are tailored to manipulate physical and mechanical properties such as size (length and diameter), attrition resistance, crush strength, pore size distribution, pore volume, and effective surface area. Catalytic performance is affected by the complicated nature of the active site and dispersion and distribution of activators and promoters. Pore size control and distribution are key factors in the behavior and formulation of residual conversion catalysts. The pore sizes need to be sufficiently large to allow the diffusion of the large residual/asphaltene molecules that require upgrading. Unfortunately as the pore diameter increases, the surface area and the hydrogenation activity decrease. The diffusion of large molecules is reduced further because of pore mouth plugging due to carbon laydown and metal sulfide buildup from vanadium and nickel atoms that are removed from the residual feed. Metal sulfides are formed from the oxidative state of the catalyst in the LC-Fining reactor environment (presulfiding reactions with sulfur in heavy oils, etc.). Catalysts are also optimized for specific functionssuch as metals removal, sulfur removal, carbon residue reduction, and high conversionwhile maintaining a clean product low in organic sediments. The catalyst system developed by BP for its LC-Fining unit at Texas City utilizes a proprietary demetallization catalyst in the first reactor and a highactivity nickel/Mo desulfurization catalyst in the second and third reactors.

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CHEVRON LUMMUS GLOBAL EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION (LC-FINING) PROCESS

EBULLATED BED BOTTOM-OF-THE-BARREL HYDROCONVERSION

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One of the key features of the LC-Fining process is the use of countercurrent catalyst addition to optimize catalyst usage. Fresh catalyst is added to the third reactor, then reused by withdrawing it and adding it to the second reactor. The catalyst can then be used a third time by withdrawing it from the second reactor and adding that material to the first reactor. Catalyst cascading results in higher overall kinetics rate constants and therefore better overall catalyst utilization based on the concentration of metals in the spent catalyst discharged from the first stage. This mode of addition and withdrawal has the added benefit of exposing the most highly converted residual to the most active catalyst. This reduces the sediment formation in the last reactor and thus allows reactor operability and conversion limits to be extended.

INVESTMENT COSTS
Compared to other residual hydrogenation processes, the LC-Fining process has several intrinsic advantages:

Very high conversion levels Low investment cost Lower operating costs Lower hydrogen losses More efficient hydrogen and heat recovery Lower maintenance

Much of the cost of a hydrogenation unit is connected to the gas recycle rate; high gas recycle rate results in high compressor, piping, furnace, heat exchanger, and separator costs. The LC-Fining process is the lowest-cost commercially proven residual hydrogenation process due to the low total hydrogen rate and the proprietary low-pressure recovery system. The low-pressure recovery system saves 8 to 10 percent of the capital investment of an LC-Fining unit, which translates to $10 million to $30 million U.S. or more, depending on plant size. Gas losses are also maintained at a low level by using low hydrogen circulation rates. When the integrated hydrotreater/hydrocracker is incorporated into the LC-Fining unit, additional savings in investment of as much as 40 percent of the cost of separate hydrotreating facilities are possible. Depending on feedstock properties, operating severities, product requirements, and processing objectives, the typical ISBL investment cost of an LC-Fining unit ranges from $2000 to $5000 U.S. per BPSD.

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