Separation Processes: P A R T 10

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
10
SEPARATION PROCESSES
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
CHAPTER 10.1
CHEVRON LUMMUS GLOBAL ON-STREAM CATALYST REPLACEMENT TECHNOLOGY FOR PROCESSING HIGH-METAL FEEDS
David E. Earls
Chevron Lummus Global Richmond, California
INTRODUCTION
In processing less expensive, high-metal feeds, the need for frequent catalyst change-outs can make conventional fixed-bed residuum hydrotreating technology uneconomical. Chevron Lummus Global (CLG) developed on-stream catalyst replacement (OCR) to remove metals from feed before it is hydrotreated in fixed-bed residuum desulfurization (RDS) units. The ability to add and withdraw catalyst from the high-pressure, moving-bed OCR reactor while it is onstream gives refiners the opportunity to process heavier, highmetal feeds or to achieve deeper desulfurization while maintaining fixed-bed run lengths and improving product properties.
DEVELOPMENT HISTORY
Development of the OCR process started in 1979 as part of the research on new reactor concepts which might be applied to synthetic fuels and heavy oil upgrading. Most of these alternative fuels are difficult to upgrade to transportation fuels. Typically high in nitrogen, sulfur, and metals, they tend to deactivate catalyst very rapidly. Consequently, conventional fixed-bed hydrotreating processes can not upgrade these feedstocks economically. CLG determined that if fresh catalyst could be continually moved through a reactor, then catalytic activity could be maintained without shutting down the unit. Theoretically, the metal capacity of the catalyst would be fully utilized in the OCR unit, thus reducing the necessary size of the downstream RDS unit and lowering total operating costs.
10.3 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
CHEVRON LUMMUS GLOBAL ON-STREAM CATALYST REPLACEMENT TECHNOLOGY FOR PROCESSING HIGH-METAL FEEDS 10.4
Using cold model and catalytic testing, CLG showed that with the proper equipment design these process improvements could be obtained. The feasibility of the process was proved during the operation of a 200 barrel per day (BPD) demonstration unit a ChevronTexacos Richmond refinery in 1985. Critical to the designs success was the proof that the valves could operate reliably at the high temperatures and pressures required for residuum upgrading.
PROCESS DESCRIPTION
CLGs OCR process is a countercurrent, moving-bed technology that removes metals and other contaminants from feedstocks prior to processing in fixed-bed residuum hydrotreating reactors. In the OCR rector, residuum and hydrogen flow upward through the reactor, and the catalyst flows downward. This process removes the metals and carbon residue that cause plugging and catalyst deactivation in conventional fixed-bed RDS units. Figure 10.1.1 shows the OCR reactor system, including the equipment used to transfer catalyst into and out of the reactor. OCR reactors can be paired and serve as pretreatment beds for two parallel trains of fixed-bed reactors. In this case, only one set of catalyst transfer vessels is needed to move catalyst for two OCR reactors.
Caalyst Transfer System In a parallel train system, catalyst transfer is done, on average, once a week to and from each OCR reactor. The amount of catalyst transferred varies from 1.5 to 8 percent of the OCR reactor catalyst capacity. The quantity removed is dictated by the nickel and vanadium content of the feed and the metals concentration on the removed catalyst. The transfer rate is adjusted to allow for changes in operating requirements. Once the requirements are defined, the catalyst is added and withdrawn batchwise on a regular schedule to maintain the required OCR activity.
FIGURE 10.1.1 OCR reactor system. CLGs OCR technology adds and removes catalysts from a high-pressure reactor while it is operating, thus providing refiners the opportunity to process less expensive, high-metal feeds.
CLG ON-STREAM CATALYST REPLACEMENT TECHNOLOGY
10.5
All the steps required to transfer the catalyst are controlled by a computer-driven, automatic sequencer. Use of the automatic sequencer minimizes the need for operator attention and ensures consistent adherence to all necessary procedures. Operation of the OCR catalyst transfer system is easily monitored by the existing RDS board operator. Catalyst transfer in and out of the OCR reactor is accomplished in a series of steps which do not interrupt the operation of the unit: 1. Fresh catalyst is transferred by gravity into the low-pressure catalyst feed vessel. 2. There, flush oil (usually a heavy gas oil) is added, and the mixture is transferred as a slurry to the high-pressure catalyst vessel (HPCV). 3. The low-pressure catalyst feed vessel is then isolated, and the pressure in the HPCV is equalized with the top of the OCR reactor. 4. The fresh catalyst is then transferred as a slurry to the top of the OCR reactor. 5. Once the transfer is complete, as indicated by the level in the HPCV, the double isolation valves are flushed to remove catalyst, and the HPCV is isolated from the system. Spent catalyst is removed from the bottom of the reactor in a similar manner: 1. The HPCV is pressure-equalized with the bottom of the OCR reactor. 2. The spent catalyst is moved as a slurry in the feed residuum from the bottom of the reactor. Once the desired amount of catalyst has been transferred, as indicated by the level in the HPCV, the transfer is stopped and the valves and lines are flushed with oil. 3. The double isolation valves are closed, and the HPCV is isolated from the OCR reactor and depressurized. The spent catalyst is washed of residuum and cooled. 4. The catalyst is transferred as a slurry to the low-pressure catalyst vessel, where the flush oil is drained. 5. The spent catalyst flows by gravity into the spent catalyst bin for disposal. Since the catalyst is transferred in a low-velocity oil slurry, catalyst attrition is prevented and the systems lines and valves are protected from erosion. OCR lines are smaller than main process lines, and special full port valves are used in the catalyst transfer lines. These valves are flushed clear of catalyst before closing, to minimize valve wear.
OCR Reactor A schematic drawing of the OCR reactor is shown in Fig. 10.1.2. The catalyst bed in the OCR unit is essentially a fixed bed, which intermittently moves down the reactor. The catalyst level in the OCR reactor is monitored by a level detector at the top of the reactor. As fresh catalyst is added at the top of the reactor, residuum is fed into the bottom. Both move through the reactor in a countercurrent flow, causing the dirtiest, most reactive residuum to contact the oldest catalyst first. The upflow of the residuum through the OCR reactor slightly expands the catalyst bed. This slight expansion enhances residuum/catalyst contact, minimizes reactor plugging, and creates a consistent pressure drop, thus providing for optimum flow patterns through the reactor. Meanwhile, the fully spent OCR catalyst is removed at the bottom of the reactor. The specially designed cone at the bottom of the reactor allows for plug flow of the catalyst to the removal port at the bottom of the reactor. This plug flow ensures that the most metal-loaded, least active catalyst is removed from the reactor. Consequently, catalyst activity is maximized and cost is minimized.
FIGURE 10.1.2 OCR reactor details. The countercurrent flow of reactants and catalyst through the OCR reactor ensures that only the most nearly spent catalyst is removed, thereby minimizing catalyst usage and cost.
Bed plugging is one of the most common causes for premature shutdown of fixed-bed hydroprocessing units. Particulates and reactive metals depositing on the top layers of the reactor cause an increase in pressure drop and maldistribution of the liquid and gas flow. This, in turn, can lead to localized hot spots and rapid coke formation. Two features of the OCR process dramatically reduce the severity of this problem in downstream fixed-bed units: 1. The most reactive feed metals are deposited on the OCR catalyst and do not enter the fixed-bed unit. 2. Particulate material in the feed is not retained in the OCR bed, but passes through to the fixed-bed unit. Separating the problems of particulates and reactive metals allows the refiner to optimize catalyst grading for the removal of particulate material in the downstream fixed-bed units. As a result, the problem of metal or coke fouling in the RDS unit is largely neutralized by the high hydrodemetallization (HDM) catalyst activity in the OCR unit. OCR units operate at the same temperature (approximately 730F) and pressure (approximately 2000 lb/in2) as their downstream RDS counterparts. Consequently, integrating OCR into the processing scheme is easy and efficient because it can use the same recycle hydrogen supply, feed pumps, and feed furnace as the fixed-bed RDS reactor.
Catalyst CLGs RDS and VRDS catalysts are developed by Advanced Refining Technology (ART), a joint venture of ChevronTexaco and Grace Davison. A special spherical catalyst developed by CLG and ART was designed to fit the requirements of the OCR process:
High hydrodemetallization activity and metals capacity to minimize downstream reactor volume and catalyst usage Moderate hydrodesulfurization (HDS) and Conradson carbon removal (HDCCR) activity to reduce coking
10.7
Strength and hardness to minimize breakage in handling Consistent shape and size to facilitate catalyst transfer and stable bed operation
Since its introduction in 1992, the OCR catalyst has exhibited low attrition, high crush strength, and exceptional selectivity for residue demetallization. The Ni V conversion typically exceeds 60 percent for the first 60 days of operation and then gradually trends toward the expected equilibrium conversion level, 50 to 70 percent (see Fig. 10.1.3). In commercial operation catalyst is withdrawn and routinely analyzed for nickel and vanadium content. This analysis confirms that only the most spent OCR catalyst is being withdrawna critical factor in minimizing catalyst consumption and cost. While the main objective of the OCR reactor is to extend catalyst life in downstream fixed-bed reactors by maintaining high HDM performance, the OCR catalyst also achieves high HDS/HDM and HDCCR/HDM activity ratios. As shown in Fig. 10.1.4, the OCR reactors sulfur and CCR conversion has been excellent. Typically, the HDS conversion stabilizes at the HDS equilibrium objective target of 50 percent while the HDCCR conversion stabilizes at the equilibrium objective target of 30 percent. The level of HDS and HDCCR activity in the OCR reactors greatly improves the overall performance of the OCR/RDS units and significantly extends the run life of the fixed-bed catalyst.
COMMERCIAL OPERATION
CLGs OCR process has been in commercial operation since 1992. The first unit was installed as a retrofit to a CLG-licensed RDS unit at the Indemitsu Kosan Company, Ltd. (IKC) Aichi refinery (see Fig. 10.1.5). Chiyoda Corporation provided the detailed engineering for the project. The RDS unit at the Aichi refinery consists of two parallel reactor trains which process a total of 50,000 barrels per stream-day (BPSD) of atmospheric residuum (AR) that is fed to a residual fluid catalytic cracking (RFCC) unit. Prior to adding OCR, atmospheric residuum from Arabian Light was the required feed. Upgrading the RDS unit with an OCR reactor enabled IKC to switch feeds from 100 percent Arabian Light to a less expensive blend of 50 percent Arabian Light and 50 percent Arabian Heavy
100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 100 120 140 HDM Equilibrium Objective Target
FIGURE 10.1.3 OCR hydrodemetallization performance. By maintaining consistently high HDM performance throughout the run, OCR reactors minimize catalyst consumption and optimize catalytic performance.
100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 HDCCR Equilibrium Objective Target 100 120 140 HDCCR HDS HDS Equilibrium Objective Target
FIGURE 10.1.4 OCR hydrodesulfurization and Conradson carbon removal. The OCR reactors excellent sulfur and Conradson carbon residue conversion enables downstream RDS units to optimize catalyst usage.
without sacrificing RFCC feed quality and fixed-bed catalyst life. Table 10.1.1 shows how the feed rate was increased, yields of naphtha and gas oil increased, and RFCC feedstock properties improved with the addition of the OCR reactors. The OCR unit also improved the activity and fouling rate of the RDS catalyst (see Fig. 10.1.6).
OCR APPLICATIONS
The driving force behind the decision to add OCR technology to an RDS processing scheme is the desire to run heavier, higher-metal feeds, because of crude oil changes or the need to cut deeper into the barrel. As the metal content of the feed rises above 100 to 150 ppm, the catalyst life cycle decreases to the point of being uneconomical. Figure 10.1.7 shows how much the relative catalyst life for a fixed-bed unit decreases as the total feed metals in the residuum increase. When OCR is added to the processing scheme, total catalyst consumption is less than that for processing with a fixed-bed unit alone. Figure 10.1.8 shows the catalyst consumption required for a fixed-bed RDS unit operating alone versus a combined OCR/RDS processing scheme. The economy of the OCR reactor is especially apparent as the feed metals approach 200 ppm. Total catalyst consumption is lower because only the most heavily loaded catalysts are removed from an OCR. In a fixed-bed reactor, catalyst with low metal loading must be discarded with the spent catalyst at the end of the run. Since only spent catalysts are removed from an OCR reactor, the catalyst is fully utilized, thus reducing the total catalyst cost per barrel of feed processed. Coincidentally, this also minimizes the amount of spent catalyst generated per pound of metals removed. The higher metals on the spent catalyst allow for more economic reclamation of the metals from the spent OCR catalysts. Adding an OCR in front of an RDS is also cost-effective when the goal is to maximize production of lighter, cleaner-burning transportation fuels. The OCR allows less demetallization catalyst to be used in the fixed beds, thus providing greater reactor volume for high-activity desulfurization catalyst. Achieving deeper desulfurization in the RDS unit enables refiners to produce ultralow-sulfur fuel oil as well as exceptionally clean feed for an RFCC unit.
10.9
FIGURE 10.1.5 OCR retrofit of Aichi RDS hydrotreating unit. The Aichi retrofit was completed in less than a month of downtime, and consisted of adding a new OCR reactor and an OCR reactor feed/effluent exchanger to each of the two reactor trains, as well as common catalyst transfer equipment.
Using an RDS unit to prepare feed for an RFCC reactor has gained wide acceptance because high-quality mogas and middle distillates can be produced with little or no lowvalue by-products. To maximize operating profitability, RFCCs require feeds that are very low in contaminant metals, carbon residue, and sulfur concentration, in addition to having feed volatility sufficiently high to fully vaporize at the feed nozzle. Metals reduce catalyst selectivity and activity, resulting in increased RFCC catalyst consumption. Carbon residue contributes to high coke yields and heat balance problems. Sulfur forces refiners to invest in expensive flue gas desulfurization equipment. Additionally, sulfur in the feed appears in the finished products. In summary, the yield, product quality, and operating efficiency produced from an RFCC unit are directly related to the quality of the feed. The OCR/RDS technology has been used to process feed for RFCC units from a variety of heavy AR feeds, including Arabian Heavy and Ratawi. Pretreating the residuum in an OCR unit enables the refiner to use less expensive feeds, achieve higher product yields, and produce better product quality while experiencing fewer feed-related operating problems. OCR can also be combined with CLGs vacuum residuum desulfurization (VRDS) technology to upgrade vacuum residuum from heavy crudes into a synthetic AR with superior RFCC feed qualities. (For a more complete discussion, see Chap. 8.1.)
FIGURE 10.1.6 RDS catalyst performance improved with addition of OCR unit. Adding an OCR unit enabled Aichi to switch to a less expensive heavy feed, besides improving the activity of the RDS catalyst.
TABLE 10.1.1
OCR Improves RDS Operation at the Aichi Refinery OCR/RDS, typical RDS run after OCR RDS, typical RDS run before OCR 45,000 RDS feed 15.1 3.1 10 52 0.34 4.7 10 15.5 61 1 year
Atmospheric residuum feed rate, BPSD Properties Gravity, API Sulfur, wt % Conradson carbon residue, wt % Ni V, wt ppm RFCC feed properties Sulfur, wt % Conradson carbon residue, wt % Ni V, wt ppm Cracking to naphtha and gas oil, LV % Conradson carbon residue removal, wt % Run cycle
50,000 OCR feed 13.6* 3.5 11 75 0.29 4.6 10 20 67 1 year
*Crude oil was 2 API lower with OCR for a substantial savings in crude oil costs; API degrees on American Petroleum Institute scale; LV % liquid volume percent.
10.11
FIGURE 10.1.7 Relative RDS/VRDS catalyst life versus feed metal concentration. (VRDS is vacuum residuum desulfurization.) Conventional fixed-bed hydrotreating cannot economically process highmetal feeds.
FIGURE 10.1.8 Comparison of catalyst consumption. Total catalyst cost is reduced when OCR technology is added to processing schemes designed to treat heavy, high-metal feeds. (Note: Based on the same reactor volume in both systems.)
ECONOMIC BENEFITS OF OCR

The most apparent economic benefit of adding OCR to the processing scheme is the ability to run heavier, high-metal, less expensive crudes. Figure 10.1.9 shows how gains in gross margin can be made by improving unit capacity while maintaining the same fixedbed investment. Similarly, when retrofitting an existing RDS unit with OCR technology, savings are achieved by extending catalyst life and run lengths. Each catalyst change-out in a fixed-bed unit takes approximately 4 weeks. The shorter run-length means a costly reduction in the on-stream factor. Thus, the penalties for processing a high-metal feed in a fixed-bed unit are twofoldhigher catalyst cost and reduced on-stream factor. OCR eliminates these limitations by providing maximum catalyst utilization and increasing the onstream operating factor to approximately 0.96. The economics of the OCR process are greatly dependent on the difference in price between light and heavy crudes, and each refiners operating constraints. At a differential of U.S. $1.80/bbl between Arab Light and Arab Heavy crude, switching from 100 percent Arabian Light to a 50/50 blend of Arabian Light and Arabian Heavy will pay back the OCR investment in less than 2 years. Alternatively, the unit throughput can be increased. In this scenario, with a product upgrade from heavy feed to low-sulfur fuel oil and to middle distillate, an increase in feed rate of 10,000 BPD will pay out in less than 2 years. More recently, CLG has also commercialized its UpFlow Reactor (UFR) technology in China. The UFR is essentially the OCR reactor without the catalyst handling equipment. As with the OCR, the UFRs low pressure drop and the reduction in pressure drop buildup during the run are particularly well suited for revamping existing units. Installing a UFR allows for the refiner to make a cheaper initial capital investment, while designing in the flexibility to invest in an OCR with the catalyst handling equipment in the future. The OCR allows for processing more difficult, higher-metals feeds with the ability to replace catalyst on-line.
FIGURE 10.1.9 Savings in HDM reactor size with OCR. Throughput capacity of RDS units increases significantly when they are operated in conjunction with an OCR unit.
10.13
OCR is a valuable technology for refiners trying to meet tough environmental guidelines within tight budgetary constraints. The benefits of the OCR process are summarized below:

Ability to process less expensive, heavy, high-metal feedstocks No interruption in operations to remove spent catalyst or add fresh catalyst to the OCR reactor Prevention of guard-bed plugging problems Longer life for downstream residuum-hydrotreating fixed-bed catalysts Reduced downtime for fixed-bed catalyst change-outs Savings in HDM reactor size Additional throughput capacity with no increase in furnace capacity or NOx emissions Lower overall catalyst costs Minimized waste from spent catalyst Economical recovery of metals from spent catalyst

Separation Processes: P A R T 10

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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 100 120 140 HDM Equilibrium Objective Target

50,000 OCR feed 13.6* 3.5 11 75 0.29 4.6 10 20 67 1 year

ECONOMIC BENEFITS OF OCR

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