II.

HEAVY OIL PROCESSING
A. Fluid Catalytic Cracking
Mechanical
QUESTlON 1. How could on stream factors be improved, and what are the most frequent causes of unscheduled downtime? Does anyone utilize a formalized program to improve FCC on stream factor? ROSS:

Many oil companies monitor the maintenance records of their catalyric crackers and develop proactive repair and replacement strategies to avoid surprises duringoperation. This is becoming increasingly important as refiners extend the run length between major turnarounds. For refiners with fewer units and less historical data, either a somewhat more reactive approach, or a conservative frequent replacement policy may be appropriate to avoid problems with older equipment results. With computer data acquisition and control now common, every refiner should be monitoring not only process variables and yields but also engineering or calculated performance parameters, such as velocities throughout the unit, to anticipate problems. Improved operator training is a must to minimize human errors and avoid stressing the equipment by staying within design and safety specifications of the equipment. Thermal scans twice a year are also recommended to monitor refractory integrity. The most often cited reasons for unscheduled downtime include: power and utility failures; compressor or turbine problems; coking in a reactor/transfer line or slurry circuit; cyclone problems; expansion joint and/or slide valve failures; cracking in hot wall components (w-ye section, standpipe, etc.); and corrosion in the main fractionator overhead system. Of course, refractory failures and human error show up on most lists as well.
ABRAHAMS:

keeping FCCUs on-line, in our case, has been the operation of the wet gas compressor. At one of our refineries, we have the luxury of having two compressors. So an outage there just results in a slowdown. Other formalized programs on the FCCUs include ultrasonic pipe thickness testing for corrosion monitoring, and thermographic surveys of refractory lined areas. We also have had either shutdowns or delayed restarts after revamping portions of our units during turnarounds, and we would recommend extra attention to modification design and installation. This has occurred both in reactor/regenerator type work and in gas plants.
EMANUEL:

Our two catalytic crackers each have their own weaknesses that are inherent in any FCCU. But in our older unit in Big Spring, Texas, the most frequent downtime is typically caused by erosion in a reactor overhead system and erosion in the slurry section of the main fractionator. This is caused mainly because we are pushing the older unit way beyond its original design. Our newer unit, which is at Port Arthur, Texas, was started in 1991 and experienced typical start-up problems. We did have initial problems with a catalyst cooler, but the main problem with that unit has been, as mentioned earlier, power failures. We are still trying to work through a problem upstream on our power system to give us better reliability. As far as items that are formalized to improve our on stream factor, we practice thermal scanning for refractory hot spots. Also, on the newer units where there is generally only one blower and one compressor, on-line monitoring for rotating equipment is becoming more and more important.
KELLER:

Some of our more frequent causes of unplanned shutdowns on FCC units have been instrument problems. One recent shutdown was caused by a broken wire on a shutdown circuit. A program to do preventive maintenance on all critical alarms and shutdowns has helped minimize this, although we have had to find the right balance at our plants between the advantages of preventive maintenance and the inadvertent trips that happen every time instruments are taken off-line. Another key to 44

On stream factors can be improved by implementing a consolidated Operating, Preventive Maintenance, and Proactive Reliability program that encompasses the following: Operator awareness and support of operating guidelines that can impact on stream reliability. Effective maintenance repair and troubleshooting, coupled with a strong PM program. Piping and pressure vessel corrosion monitoring. Vibration monitoring and oil analysis for critical rotating equipment.

Heavy Oil Processing

On-line monitoring systems (critical variables, performance trending, etc.) for critical equipment, Infrared thermography for mechanical and electrical equipment. Sound root cause failure analysis and solution engineering to reduce failure re-occurrence. The most common cause of unscheduled FCC downtime is heat exchanger failure (leaks due to corrosion, fouling, etc.), especially in the associated HF alkylation and butamer units. Yes, most refineries utilize formalized reliability programs that include some of the elements mentioned in the list above. It is rare, however, to find fully integrated/comprehensive programs that derive the maximum on stream benefit that is achievable.
QUESTION 2. What parts of the unit become susceptible to failure when operating with run lengths greater than three years? DEADY:

on those three units, roughly 50% of the unscheduled outages were related to failures of the cyclone systems. Approximately 30% of the outages were related to slide valves or transfer line problems. And the remaining 20% were miscellaneous other failures, e.g., expansion joints, compressor, and rotating equipment type items. We are also on a 4-year cycle at Lake Charles.
KELLER:

Our total downtime is 8%. We have a planned turnaround that lasts a month and a half, every four years. That is 3%. All the unscheduled downtime adds up to the remaining 5%. That is 1% for heat exchangers; 0.6% for the main air blower and expander; 0.1% for the reactor regenerator cyclones, the riser, and the air grid nozzles; 0.3% for the flue gas cooler and piping; 0.2% for the reactor steam rings; 0.8% for the compressors; and all other causes account for the remaining 2%.
POTSCAVAGE:

I have a laundry list of the areas of the FCCU that generally provide the most trouble after long run lengths. The first is refractory problems where refractory is coming off and plugging catalyst circulation lines, or causing hot spots or bulges. The feed nozzles may also show wear and/or plugging. The slide valve or plug valve can have damage or erosion, and there may be damage to air grids or air rings. We have also seen damage to ESP plates and wires, regenerator stack valve damage, and erosion damage to the expansion joints.
EMANUEL:

The top five problems we experience are refractory failures, primarily in catalyst transfer lines; reactor overhead lines, as I mentioned earlier; flue gas scrubber ducts; regenerator cyclone lining problems, in the older units; and major rotating equipment such as the blower and wet gas compressor.
FRONDORF:

Corrosion can cause premature failures of equipment in a main fractionator overhead and the saturated gas plant. When we talk about corrosion, it is typically not general corrosion but rather hydrogen blistering that is the major problem. In trying to control hydrogen blistering, make sure you have an appropriately applied water wash. We will talk more about that in one of the later questions. Also, try to have a filmer in use that is designed specifically to deal with hydrogen blistering. For example, the filmers used on crude unit overheads are not effective at controlling hydrogen blistering. And having a good monitoring program is imperative. There are some on-line monitors available in the marketplace. Preferably you should have one that is hooked up to a data logger to determine non-steady state hydrogen blistering activity. The most reliable, accurate, and easy to use monitor we have seen is our HPC-11. It is readily moved from location to location, gives a quick response, and hooks to a data logger to help monitor non-steady state conditions.
ROSS:

In our Corpus Christi, Texas refinery, we are on a 4-year turnaround cycle on the catalytic cracker. We concur with several of the other problem areas that already have been mentioned. We would add that on units with a power recovery train, the expander will definitely become an issue. On single stage expanders, primary blade erosion has been prevalent, and on multi-blade units, secondary blade erosion may be expected. We have also, over the years, experienced problems with expansion joints, particularly the flue gas expansion joint. At Lake Charles, Louisiana we have three identical catalytic crackers without power recovery trains. Reviewing our unscheduled outage history for the last 25 years

Although many refiners target 4- to 5-year runs, most anticipate a short 2-week shutdown midway into the run for minor repair work on chronic maintenance problems such as cyclone erosion; refractory repairs; compressor seals; and expansion joint and slide valve inspection/repair. Flue gas systems including tertiary cyclones, CO boilers or incinerators, scrubbers and ESPs should also be inspected either as preventive measures or due to regulatory requirements. Although thermal cycling is one of the major contributors to refractory and equipment failures, a planned shutdown for inspection and preventive maintenance is generally considered prudent.

1995 NPRA Q&A Session on Refining and Petrochemical Technology

45

SHEN:

There was an industry-wide survey conducted about two years ago. The results show that there are two main causes that contribute to about 90% of the unit shutdowns; 55% are caused by cyclone erosion and 35% are caused by rotating equipment failure.
JAMES D. WEITH (Unocal Corporation):

time if it needs a change out during turnaround. We have had no failures in recent history, to my knowledge.
ABRAHAMS:

I am a representative of the other refinery in Wilmington, California, (re: Mr. Keller), and we are proud of the fact that between our February 1992 and February 1995 turnarounds our catalytic cracker had a 97.1% on stream efficiency. Of the 2.9% of the time it was down, 1% was due to six different electrical power outages, 1.5% was because of flue gas steam generator leaks, and the remaining 0.4% was due to miscellaneous mechanical problems.
PETER G. ANDREWS (Consultant):

On the last couple of questions several people have talked about power failures as though they are beyond people’s control, and in many cases they are. But one of the things that we have found useful in answering power reliability problems is to apply a little science and take a reliability view of it, going through the fault tree analysis and looking at the individual components. While many refineries are susceptible to main power grid failures from outside, a lot ofshutdowns are within your own hardware. You can determine the odds of those and focus on the weak spots to improve reliability.
QUESTION 3. Has anyone experienced weld cracks in stainless steel strip-lining in main fractionators? What was the cause? What changes in material selection or application can alleviate the problem? VAN IDERSTINE:

Both Questions 11 and 12 are similar, and you can cite anything on the FCC menu as to what shuts you down, all being unit-specific. Mr. Shen confirmed my experience: the major causes of FCCU shutdowns are cyclones and rotating equipment. With this knowledge, review your specific FCCU operation to determine if a revamp/redesign is necessary to eliminate unscheduled shutdowns in these two major areas.
DAVID S. McCAFFREY (Exxon Research & Engineering Company):

Questions 11 and 12 are related and my comments apply to both. Exxon’s FLEXICRACKING units are designed for run lengths of more than three years, and in fact four-plus-year runs are becoming common. In these units, much attention is paid to the design of critical components like slide valves, cyclones, reactor riser and transfer lines, regenerator grid, and the various vessel and grid penetrations. We found that the major factors impacting run lengths are: running at conditions above a unit’s design rates and starting up after a turnaround with worn hardware. We do have a systematic research and development program for reviewing the conditions of units as they have turnarounds. The objective of this program is to upgrade service factors and reliability. The results from this program are continually incorporated into all our new designs.
MARK GREGORY (Koch Refining Company):

We have a fractionator that has a 1/8" type 405 ferritic stainless liner from the heavy cycle oil draw down to the bottom head. We have had that situation since 1961, and we have not experienced any problems with that clad lining. The maximum width of the strip lining is dependent on the maximum operating temperature in the vessel. For a temperature range of 950°F to l000°F, the maximum width should be 3” and the maximum length 36". Each strip should be welded to the vessel shell individually with a fillet weld. Adjoining strips are placed so that they are welded directly to the shell. One final weld pass should fill the cavity between the two fillet welds.
KELLER:

Our FCC main fractionator was built 13 years ago. It was originally clad with 410 stainless steel. We have had no history of weld cracking.
ROSS:

My question regards expansion joints and flue gas lines. Are they typically run to failure or are they scheduled for routine replacement on a set interval?
PARKER:

Thermal cycling, temperature excursions, and high sulfur feed operation can result in cracking in the cladding. Once the cracking begins, further work or maintenance becomes problematic, and ultimately replacement is required.
REZA SADEGHBEIGI (RMS Engineering, Inc.):

Most of the flue gas expansion joints we are now installing are double ply, and we can check the inside wall to see if it is leaking on the run. So we can tell ahead of

Weld cracks are primarily caused by thermal expansion of the stainless steel lining. Our recommendation would be to install a 410 SS clad in the bottom section of the main fractionator.

46

Heavy Oil Processing

QUESTION 4. Our regenerator flue gas pipe is unlined and it must be replaced soon due to corrosion. What are the pros and cons of installing a cold wall flue gas pipe versus staying with the original design? Has anyone made this type of conversion? SOLIS:

EMANUEL:

Our regenerator flue gas overhead line is lined through the waste heat boiler and orifice chamber. Downstream of the orifice chamber, we go to a hot wall design. We have not experienced any problems in the unlined section. In my experience with other catalytic crackers, I have never really seen a major problem with a cold wall design.
KELLER:

Our flue gas line is hot wall, with internal lining of ¾" abrasion-resistant lining-castable (hexagonal mesh) and externally isolated. No corrosion has been seen, but we have had serious stress problems, causing a complete redesign of the whole line. We have installed new expansion joints, relocation of spring support, and 80% are new ones. It is common practice today to use a cold wall design for the regenerator flue gas line. The advantage of this is less thermal expansion, and the piping run is easier to design with fewer expansion joints. Problems with 304 SS stress corrosion cracking are eliminated. The disadvantages of the cold wall design are the larger size pipe required due to the internal lining, and the increased weight for support. If an existing hot wall flue gas duct is to be replaced with a cold wall design, the routing of the duct must be checked to see that the larger size will fit properly in the pipe rack.

Ultramar made this conversion in December 1993 after experiencing creep cracking in the original hot wall line. The line was 11 years old. The new line with the cold wall design operates at 300°F to 500°F and is more forgiving to process temperature excursions. We expect to get a 20-year life on this installation, and it is the technology advocated by UOP. The reliability of the cold wall design depends on the integrity of the refractory lining. One small failure in the lining requires immediate identification and external cooling, or it will result in an unplanned FCCU shutdown. The installation of the cold wall design requires about 10% more expenditure and additional engineering time to make the modifications to the pipe, structure, and hangers.
QUESTION 5. What new methods are refiners using to clean fouled slurry exchangers, (e.g., on-line cleaning, chemical washes)? Have slurry antifoulants been used successfully? POTSCAVAGE:

We are not familiar with any on-line cleaning or chemical wash type approaches that can be utilized to clean slurry exchangers. This is probably because the chemical composition of the slurry itself results in fouling material that is typically very tenacious. From the standpoint of the slurry antifoulants, we have seen them work successfully in some situations. In some slurry systems, the operating conditions and the slurry’s physical properties are so severe that the slurry antifoulants have difficulty actually doing what they are intended to do. It is not uncommon for a slurry antifoulant to need assistance by controlling some unit operating parameters. A key parameter is the velocity of a system where 8 fps co 10 fps is ideal. Over 10 fps typically starts to cause erosion in exchangers. Controlling viscosity is also important. The viscosity target varies from unit to unit.
ROSS:

The refiners I have spoken to are very familiar with the chemical additives, but few seem to be using them. The usual operational techniques described in previous Q&A's relating to tube velocity, temperature, residence time, composition, and elimination of recycle are generally followed with good results.

1995 NPRA Q&A Session on Refining and Petrochemical Technology

47

If you get out of those ranges. We found this to be as effective. been marketed through ELF and Total. which was selected by the chemical vendor based on testing of our slurry. HANSEN: We have successfully used an antifoulant program in the slurry loop for several years. Since they instituted an antifoulant program. generally. Our rule of thumb is a little bit lower than the velocities mentioned earlier. they are able to operate without a spare and run continuously for three plus years. and were easily removed by hydroblasting. JONES (Turner. The first is periodic flushes with a hot light cycle oil (LCO) to dislodge the sludge. It probably would have operated longer. Another interesting method that has been used successfully in several refineries has been piping of the nonspared slurry exchangers to be able to reverse the flow periodically. Another refinery was shutting down every 2 days to clean the slurry exchangers. the one that sounds the most promising is monitoring of the C7 insolubles (asphaltenes). people tend to control to between 2% and 5% and have fairly good results without fouling. If you stay in a certain range. We do have the LCO hot flush connections that Mr. We have increased our focus on maintaining adequate exchanger tube velocities. As I understand from the literature. We periodically back flush the slurry exchangers on-line. EMANUEL: I do not have a horror story quite that bad. However. if you look back over the last several years at all the techniques to monitor operation andcomposition. 3% of the naphchenic-type crude into that will usually be the limit. When they switched to a good slurry antifoulane program. There are also in-line scraping systems. With this arrangement. Ross mentioned. This type of program significantly reduced slurry exchanger fouling in one refinery with which we are familiar. The fouling deposits were loose and mainly catalyst. We also control the slurry gravity to about -5” API. For a few minutes each week the flow is actually reversed through these exchangers and the deposits that are building up are broken free and caught within filters. The program was originally started to reduce and control fouling in the packed sections of the main fractionator. which have required mechanical cleaning. the use ofgood filters at the exchanger inlets is mandatory. We control between 4 fps and 7 fps.): Depending on the configuration of the FCC bottoms pumparound. you can go up to 15% paraffinic material. As a cost reduction method. usually antifoulants will work. and sometimes more effective. Inc. This procedure has a strong analogy to what is done to monitor primary fractionator fouling in ethylene plants. There have been instances when excessive catalyst carryover has caused fouling of the slurry loop steam generators. to continually break free deposits. That tends to be on a yearly cycle.Two methods have been mentioned in the past. they are not necessarily very effective in cleaning an already fouled system. We still have not been able to justify the antifoulants in slurry service. JOHNS: Fouling will usually occur two ways: from coking and from asphaltene precipitation. I have a couple ofstories from refiners who have been successful in using antifoulants. the shutdowns have been more on the order of 9 to 12 months. an antifoulant will not work. with a caution that you break free almost all the deposits in the circuit and you have a good filtering system. we stopped adding antifoulant into the system and did not see an increase in our fouling frequency. with the napthenic crude. The program uses high temperature dispersant and inhibitor chemistry. that seem to be the most frequently used to clean the systems. the pumparound system operated continuously for about 27 months. A rule of thumb on the asphaltene precipitation is that if you are using a charge from highly paraffinic crudes. with polymer chunks collecting in a good filtering system. Mason & Company): Generally we think that slurry antifoulants will do a good job of preventing the pumparound system from fouling. REZA SADEGHBEIGI (RMS Engineering. an effective on-line cleaning could be a continuous injection of 3% to 5% of either HCO or LCO 48 Heavy Oil Processing . Antifoulant programs that provide on-site technical service do improve operator control over unit operating parameters. In every instance. which have. Once or twice a year we use that system for a period of five to eight hours to circulate hot LCO flush back to our fractionator. I have heard from one refiner that occasional use of a heavy naphtha has been used. Above that you will get precipitation of asphaltenes in hot slurry exchangers and preheat heaters. Finally. but the unit went down for a scheduled One thing that has not been mentioned is that good control over your main column bottoms temperature can prevent a lot of slurry exchanger fouling. DEADY: turnaround. than the use of antifoulants. So we revised our piping so that we can pull exchangers one at a time and hydroblast while the unit is on-line. but that tends to have a fairly small effect. VAN IDERSTINE: Our fouling of slurry exchangers has dramatically decreased in the past 2 to 3 years. One was operating a slurry system that had to be shut down about every 11 months to clean the fouled exchangers. perhaps not quite so new. JAMES W. On the other side.

MAT. we are very satisfied with the quality of our supplier. This provides a reference point for specifications and vendor tests on the new catalyst because there are such discrepancies between the different vendor tests. The quality control program to carry out with the samples has been previously agreed upon with the catalyst producer. in which a supplier was unable to deliver suitable quantity and quality of a new catalyst. ROSS: We have developed a very extensive process of selection before any changing of catalyst. Typically. we parted ways for a couple of years and went with another supplier. PARKER: Generally. and typically before we run any new catalysts in the unit they conduct a full range of fresh and de-activated catalyst property tests. If you do not. and we have only observed problems on two occasions. If the sample does not meet specifications. metals level. Be sure to cross-correlate. we conduct testing at our research center. and perhaps operation in a pilot unit using the feedstock from the unit in question. we call the vendor and usually we are compensated on the next shipment or by making a price adjustment. Properties such as pore volume. We receive most of the tests listed on the data sheets for each shipment with the exception of attrition. The test always includes MAT Activity (>72%). We rely heavily on our supplier’s analysis and crosscheck periodically. so we do test our ECAT when we receive it. We call and usually get an adjustment toward the target value. we can reject the truck or ask for liquidation damages. Once in a while we will put equilibrium catalyst (ECAT) in our resid cracker. though. Average values of variables can be monitored. Once we have selected the vendor. chemical composition. Catalysts QUESTION 6. One refiner cautions that particle size distribution can be tricky as sampling a large truck is not trivial due to settling/segregation during transit. Results of these tests are then discussed with the catalyst vendor. but continuously on the low side of the range on a particular property. We also have been very successful in dealing with the vendors directly for recourse on the rare occasions we have had problems. One problem that we have had occasionally is that we may be getting material that is within specifications. We do compare these numbers to the specifications we have for our catalyst. rare earth. chemical composition (zeolite. alumina. fresh catalyst is sampled randomly or each batch received is sampled with samples retained but tested randomly by the refiner’s central laboratory or research and development facility. We have developed a procedure in which we take one sample from the truck for the supplier. to track consistency and control of the process to identify irregular batches. and particle size analysis are performed on perhaps 20% to 30% of the samples. One was low attrition and the other was a case where they sent the truck to the wrong refinery. you will have serious problems comparing results. We have had instances where we had Some refiners rely on the quality assurance programs and certifications of the catalyst vendors. as well as possible. we monitor the fresh catalyst using the data sheets from the vendor. Na2O (<0. ABRAHAMS: Our practices are similar co those of Mr. or if there is a discrepancy with a vendor. possibly resulting in compensation. How is the quality of fresh FCC catalyst monitored by the refiner? What is the frequency of testing? What are the properties monitored and what tests used? What is the recourse for qualify problems? SOLIS: to reject shipments based on samples.into the inlet of the bottoms exchangers. whereas others are more proactive. one as reference and one for testing. Generally speaking. Sophisticated high-volume users may request vendor process control charts and trend manufacturing control points and variables. Response times of about one week are reported. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 49 . There was one instance a few years back. One of the major concerns of this program is sampling. etc. We have really not had many problems. and promoter/platinum content). Parker. If we suspect a problem. the analytical methods of the refiner and the catalyst supplier.45%). samples are sent to the research and development or central laboratory for independent analysis of MAT. As for ECAT analyses. and Attrition Index (DI<8). Those are only done occasionally. If there is a problem.. maybe every third or fourth truck. They can test all the properties. and surface areas. While it was painful. You may also want to have a spare bundle on hand to minimize downtime. We have developed this program over six years. Good sampling and sample retention procedures are essential. surface area. samples are taken either weekly or twice a week for analysis by the vendor. we include a clause in the purchase order that we have the right to take samples of the fresh catalyst that they supply. This process is designed to choose the optimum catalyst for our feedstock and unit operating conditions. as well as deviations from the manufacturers’ set points. When unit performance changes unexpectedly. attrition index.

especially particle size and attrition and catalytic testing to measure activity and coke selectivity. In several instances. STEVEN K. 1995.. PETER G. XRD. WILLIAM D. the X-ray diffraction analyst was the first to identify changes in the fresh catalyst composition. TCLP.): of potential contributors. Fresh catalyst shipments are routinely sampled and tested. In any case. HIGGINS: Could we have a show of hands of who tests fresh catalysts all the time? The audience show indicates five or six. We collect both vendor lot samples and truck samples of the fresh catalyst at the refinery. the items of major interest are the fresh activity. but most of that has been discontinued due to refinery and research and development cutbacks. PAVEL (Coastal Catalyst Technology. in certain cases. Some refiners without internal laboratory facilities have sent random samples for third-party testing. we would change suppliers if we felt we had a problem. QUESTION 7. but also the capabilities and driving economics of the FCC catalyst manufacturing process. There are economic penalties associated with falling outside of some of these ranges. surface areas. and to provide a qualitative analysis of mineral composition or phase. without analysis of the fresh material it is difficult to calculate the deposition of contaminant elements.): We monitor fresh catalyst quality in a central technical support group and laboratories. The refiner also needs to make sure they obtain a representative sample for testing. we also conduct attrition and particle size distributions tests. and full MAT yield tests unsteamed and after steaming for 4 hours and 16 hours. or a catalyst that does not meet specifications. and they were also summarized in the Oil and Gas Journal. HANSEN: We also generally rely on the quality control sheets provided by the catalyst suppliers. and previous deliveries. It is generally accepted that “any system under observation changes. ANDREWS (Consultant): Most refiners have operated for a long time without testing fresh catalyst. Several others have in the past. The refiners who still do their own analyses analyze every shipment. by ICI? X-ray diffraction is used to measure unit cell size and crystallinity. pore volumes and pore size distributions by nitrogen and mercury. catalyst formulation changes or catalyst additive use)? DEADY: Previous responses illustrate the importance of testing refinery fresh catalyst deliveries to avoid getting a rogue delivery of a catalyst meant for another refiner. We have worked closely with our catalyst vendors and have put in place quality control agreements for various composition and physical properties. Typically. particle size distribution and attrition. HENNING (Conoco Inc. Profiles on new catalysts might include: XRF. Fresh catalyst elements are analyzed by XRF.DEADY: A handful of our customers continue to monitor fresh catalyst properties. Analyses of feedstock elements usually do not include all the deactivating contaminant elements in the feedstock. Fresh catalysts are a source of the spent catalyst elemental constituents. What success have refiners had at reducing FCC naphtha olefins wifhout losing octane (e. We have found the need on occasion to send samples to third parties to confirm shipment quality and. I might add that a refiner seeking a formal quality agreement with their catalyst vendor should understand not only what catalyst properties are important to their unit. to eliminate fresh catalyst from the list Many of the ways that refiners can reduce FCC naphtha olefins have been discussed in the 1994 NPRA Q&A Session transcript. Terry. reactor riser temperature. There are specified ranges for each shipment and a narrower range for a six truck moving average. Delivered fresh catalyst properties are compared to specifications. Most often problems are detected in the unit. particle size distribution and hardness. rare earth. We have found in the past that some incidents of FCC performance loss have correlated to catalyst quality. bulk and skeletal density. each truck sample is tested for composition by x-ray and for surface area. Inc. testing and analysis are essential. Minimum testing includes XRF and XRD for complete elemental analysis and crystallinity on each delivery. and. If a fresh delivery shows a significant change in XRF or XRD results.g. like most. One important caveat before starting this kind of testing would be to establish a correlation with your supplier’s laboratory analysis. April 24. In our case. units with high addition rates relative to the size of the circulating catalyst inventory ate most sensitive to fresh catalyst property changes. pore volume by water. The properties they monitor include chemical and physical properties. which are deposited on the fresh catalyst either routinely or as a spiked anomaly. it would be of interest to know how many refiners are now testing catalyst all the time. This would eliminate potential laboratory biases due to analytical differences and allow you to establish a baseline should discrepancies arise in the future. shipment inspection reports.” The occurrence ofquality control situations can only be determined by sampling and testing. more testing is performed. 50 Heavy Oil Processing . For some units.

based on our circulating riser pilot plant testing. We hope to use the NIR technique for process control. I would add that if you have an FCC feed hydrotreater. any loss in FCC naphtha octane due to increased severity could be overcome by recycling LCO to the hydrotreater. a reluctance to drop the reactor temperature more than 10°F. is very erratic. Olefins have been a problem for us. some refiners would like to maintain gasoline volume and increase octane without increasing olefinicity. This additive technology converts gasoline sulfur species to H2S. BCA-105. the percent reduction we have observed in microactivity testing has been somewhat higher than what we have observed in riser testing. The range of matrix surface area tested was from about 20 to 125 meters squared per gram. From past experience. In fact. We saw no other changes in any of the other yields or the gasoline octanes. we would recommend switching to a high REUSY catalyst plus ZSM-5. In these cases. There is also. In MAT testing. G. In commercial units. i. The EPA-approved method had the poorest reproducibility. we have seen that changing from a low hydrogen transfer catalyst to a high hydrogen transfer catalyst will reduce gasoline sulfur by about 6%. you can reduce olefins by increasing hydrotreat severity. However. increased flue gas SO x emissions)? DEADY: We were one of the “lucky” refiners that were constructing a catalytic cracker during the 1990-91 time period.e. The switch to REUSY will reduce gasoline olefins by about 25% on a relative basis with an octane penalty of about two numbers. to maintain or reduce bottom yields while maintaining or increasing gasoline yield with the lower reactor temperatures. QUESTION 8. refiners should use moderate reactor temperature. so we had to apply for a “Work In Progress” adjustment in our refinery baseline. If the hydrotreater has the capacity to This year we completed two refinery trials of our GSR technology for gasoline sulfur reduction described in recent NPRA papers. we observed up to a 25% reduction in full range gasoline sulfur. We have tried moving reactor temperature moderately. The ZSM-5 addition will easily recover the loss in octane with no increase in gasoline olefin content. increase catalyst rare earth level to increased zeolite unit cell size.. We normally attribute this to the difference in contact time between the MAT and the riser. Currently we control olefins by maximizing catalyst-to-oil ratio in our FCC unit. but have not seen much change in olefins. especially the coke yield? Are there any other operational impacts (e. I would like to comment that the EPA approved method for testing olefins in gasoline works fairly well for blended gasoline. Regarding conventional FCC catalysts. a combination of these approaches is probably necessary. maximize catalyst-to-oil ratio.To reduce FCC naphtha olefins. LEUENBERGER (ARCO Products Company): We recently completed a test run at our Los Angeles refinery where we analyzed olefin content using the EPA method. we do not always observe a significant reduction in gasoline sulfur when the matrix surface area is increased. This reduction was corrected for changes in feed sulfur and gasoline end point. Hansen has indicated. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 51 . and use ZSM-5 to crack naphtha olefins. we have customers who have reduced the reactor by greater than 10°F. which have a higher percentage of olefins. Matrix surface area also impacts gasoline sulfur. We know of other refiners who are already using REUSY catalyst. depending on the base octane level. I would like to have some comments from the floor if anyone else has had that same problem.): While we agree with everything the panel said. and high silica-to-alumina ratio pentasils offer this possibility. But we have found that the test for streams such as light catalytic naphthas. A drop of about 30°F in the reactor temperature will decrease gasoline olefins by about 8% relative and an addition of approximately 7% olefins plus ZSM-5 containing additive will maintain octane and LPG olefins relative to the base. some studies actually show a decrease in gasoline olefins with the addition of ZSM-5. and a GC technique. ANDREW SMITH (INTERCAT Inc.. We have scheduled a trial of ZSM-5 early next year to see if that will help us. an NIR technique. Deady mentioned to control olefins. In the commercial trials. 10°F one way or the other. What level of sulfur reduction in FCC naphtha is possible by changing FCC catalyst? What is the impact of this Change on other FCC yields and properties. minimize catalyst matrix surface area. we have seen a correlation in gasoline sulfur reduction with the steamed matrix surface area ofcatalysts. ERNEST L. as Mr. They are adding a bottoms upgrading additive. compared to the low matrix surface area catalysts. then add ZSM-5 to regain the lost octane and LPG olefins. EMANUEL: handle extra feed. In order to reduce FCC naphtha olefins without losing octane. In addition to the methods that Ms. If a refiner is currently using a low or no rare earth USY catalyst. The yield shifts associated with increasing matrix surface area depend on the specific type of matrix surface area. they are planning to drop reactor temperature. The higher matrix surface area catalysts gave a 15% to 25% sulfur reduction. Further commercial testing is scheduled while work continues on improving the performance of GSR.g.

Naphtha S Reduction (%) 5 15 25 Feed FQP 76. At low conversion with some aliphatic species containing sulfur in the gasoline. S. the ability to achieve the hydrogen transfer or react out the sulfur would seem to be much more likely than at high conversion where most of the sulfur species would be aromatic. there is a reduction in the gasoline olefins. the cement manufacturers really do not care much about the particle size distribution since cement is fairly fine. and aniline point) and the feed sulfur content.5% absolute reduction in light catalytic naphtha with the heavy naphtha unchanged. if any. We have seen on a variety of catalysts up to 10% reduction in FCC naphtha sulfur. although most of the sulfur is retained by the additive and hydrolyzed to H2S in the stripper. Usually. at present it would appear that feed treatment would be more effective. at this time.but can include better bottoms cracking with the penalty of increased coke and dry gas. increasing the SOx emissions. increasing catalyst matrix surface area may not be a practical option to reduce gasoline sulfur. the extent of that reduction strongly depends on the feedstock (crude source.. I have to mention that the European auto/oil program will result in a sulfur reduction The current disposition for FCC catalyst fines is similar to that for FCC equilibrium catalyst. The refiner avoids having to deal with significant selectivity changes in the base catalyst. Also. reduction of sulfur occurs. in our short residence time cracking pilot plant work.). As an interesting aside. similar sulfur reductions were observed. sulfur content. 1. changes in rare earth (RE) content and/or different matrices. Obviously. the technology is new and developing. We have also commercially tested a proprietary sulfur reducing additive in one of our units.e. Generally speaking.4 MON. very little. Although the fine-tuning of sulfur levels may be possible via this route. particularly with very high matrix surface area catalyst.8 79. But there seems to be the following trade-off with constant catalyst-to-oil ratio and riser temperature. VABP. most of the sulfur removed is assumed to be in the form of H2S. JOHNS: I would cite some pilot unit testing at our Port Arthur research facility. QUESTION 9. SOLIS: Thus. resulting in an octane loss of 0. the results of the sulfur balances have not been released. When using specific additives for sulfur removal.3 0. and a 10% relative increase in the coke yield. Also. i.5 S% 1. possibly those creating stable aromatic sulfur species. even finer than FCC fines. The other benefits include improved bottoms upgrading and reduction of slurry viscosity. An important consideration is the conversion level at which the sulfur level reduction is attempted. However. When attempting to attack the aromatics. ANDREW SMITH (INTERCAT Inc. ROSS: in gasoline.7 Circulating pilot ‘plant work by one refiner has confirmed the 20% target reduction in full range gasoline sulfur when using these additives.2 81.9 1. we have achieved reductions of gasoline sulfurs ranging from 20% to 30% with a significant portion coming out of the heavy gasoline cut. For cement use. reductions up to 35% are achieved. etc.5 wt% for a naphtha sulfur reduction of 15 wt% to 20 wt%. EBP. a 3% absolute reduction in conversion.): In recent trials of INTERCAT’s bottoms upgrading additive. coke yield increases 0. On the other hand. What are the current dispositions for FCC catalyst fines?Are there anyproperties of the fines that restrict the method of disposal? DEADY: I will add new information on this subject based on recent pilot plant work. has been theorized. However. A reduction in secondary reactions. There were no changes in coke and C2 minus gas yield.6 RON and 0. Refiners directly attribute these reductions to the use of the additive and not to cut point changes. coke production will likely increase. However. we have observed a linear relationship between the FQP (feed quality parameter. e. and this reduction will very much affect the FCC naphtha as a component of the gasoline. Finally. the present catalysts (additives) seem to simultaneously increase the coke and H2 yields. If the FCC unit is constrained by the air blower or gas compressor. As a matter of fact. and these are only pilot plant results reported by one refiner. G. there is also some dilution effect as the gasoline selectivity is increased at very short residence time. You can either use it in cement or use it in asphalt as road base. high rare earth and high matrix activity catalysts tend to reduce the sulfur the most. sulfur reduction is clearly below 15%. which depends on feed density. and the naphtha sulfur reduction achieved. The sulfur is observed to go to H2S and LPG products rather than to flue gas. some still goes to the regenerator. By changing the actual commercial catalysts.g. 52 Heavy Oil Processing .. in some cases. That is the major reason we concentrated on the additive approach to reducing gasoline sulfur.

monitoring and regularly unloading third stage cyclone catch vessels to avoid flooding. What probably will cause a problem is that the fraction below 10 microns must be minimized. such as jets from instrument and equipment purges. I agree with most of those comments. and considering SO3 reduction methods as condensibles in the flue gas impact on the opacity. if cyclone flooding is the problem. and in Europe. we are not aware of any restrictions on the particle size. In the U. so I am not sure how practical this use would be for FCC fines in Europe. High-velocity jets generate fines which increase the overall loss and disproportionately increase the opacity reading. August 28. changing to a more attrition-resistant catalyst with a higher particle density. sometimes the corona current on the precipitator will be impacted by the 1995 NPRA Q&A Session on Refining and Petrochemical Technology 53 . otherwise they would form a cake. which is sold to a local landfill. In Europe they have restrictions on the particle size distribution. where there is an electrostatic precipitator operation downstream. ROSS: Current disposition of FCC fines from both our refineries is to landfill facilities. organics. which will impact how well the precipitator will pick up. then you probably do have an attrition source in your system somewhere. ensuring that the purged media is hot and dry and the mirrors are clean. FRONDORF: Process QUESTION 10. etc. regarding flue gas concentration. monitoring your 0 to 40 micron size in your equilibrium catalyst is important.. reducing fresh catalyst addition and fines content of the fresh catalyst. Other preventive actions include: continuous catalyst addition to avoid bursts of high losses. There are no other restrictions at this time. VAN IDERSTINE: We currently dispose of the fines caught in the underflow system with the equilibrium catalyst. The usual operational changes made to reduce catalyst losses and stack opacity include: reducing air rate (not a good choice). On the topic of attrition. which would be unusable at either facility. fortunately. and. There are metal limits in Europe as well: 4000 ppm nickel. must be checked and rechecked. KELLER: Our dry FCC fines are transported by pneumatic truck to a local cement manufacturer and “blown” into a dry hopper for later mixing. the major limit appears to be vanadium at about 8000 ppm to 10. The metals levels are 4000 ppm nickel.000 ppm. This would presumably be the same for the fines. We also collect fines through our wet flue gas scrubber system. In Europe. Wet fines are segregated from dry fines. reducing regenerator bed level. 8000 ppm vanadium. to avoid bursts of losses. I would emphasize the verification of the regenerator level as probably one of the most important and first things that an operator or engineer should do upon realizing high catalyst losses are occurring. we have experience with this application in Europe and over in the Asia-Pacific area. there are some metals limits on the equilibrium catalyst (ECAT). and continuous sonic-type soot blowers. 1995. We have also disposed of this as a nonhazardous waste and have used it in cement manufacture. HANSEN: The issue of troubleshooting catalyst loss problems has been summarized from time to time and most recently by Akzo in an Oil & Gas Journal article. FCC fines are classified on a characteristic basis per normal EPA guidelines such as metals. The characteristic classification has been nonhazardous industrial waste for typical fine properties of today. Again. 7000 ppm vanadium. increasing regenerator pressure.S. instead of daily mechanical soot blowers. there is a limit of about 7000 ppm nickel on the ECAT or the fines. not on a definition basis such as sewer sludges or waste water sludges. Very often. an overlooked attrition source is the actual cause of high opacity problems.S. All possible attrition sources under direct operator control. If the quantity in that size range is either stable or increasing during periods of high catalyst loss. and 1500 ppm antimony. These are collected separately and sent out of the plant as a nonhazardous waste. Wet FCC fines are transported to a different local cement manufacturer and bottomdumped into a liquid holding tank equipped with a mechanical mixer. What corrective actions can be taken in the operation of an FCCU to reduce the flue gas opacity? Please address only the operating aspects and not downStream equipment or technologies. Periodically we explore disposition to cement kilns when economical and available. PARKER: On the catalyst issue. In the Asia-Pacific area. and 1500 ppm antimony. or replacing oxygen enrichment for some of the air. As for using the fines in road base. so fines are probably appropriate for this use. regular inspection and maintenance of the opacity meter itself.We currently have discussed this application with cement manufacturers both in the U. you can alter the catalyst and sometimes that will change the electrical resistivity. Cement manufacturers worry about the vanadium content because it could attack the brick in the calcines and cause deterioration. Also.

Several years ago we ran into one unit that typically maintains a 50 co 55 average particle size and retains 30% to 35% of 0 to 40 micron catalyst. Also. R. air distributor. Ed Tenney of GE Environmental Services and asked what design was used for these cyclones to give that kind of retention. Several models exist that allow the quantification of attrition index.86 0. you might have uncovered the cyclone diplegs. a couple hundred pounds. They said they did not. You might want to verify the regenerator catalyst inventory levels. and sometimes.95 0. I have not received an answer yet. So even though it is directionally a good idea to change catalyst resistivity. If you use too much promoter. KELLER: We are particularly sensitive to the overuse of CO promoter. The particle sizes that contribute most of the measurement ofopacity are products ofcatalyst attrition. HANSEN: FCC flue gas opacity is caused mainly by the amounts of fines originated in the process and the type of technology to separate those fines from the flue gas. which causes erosion. but they made little catalyst off it or the electrostatic precipitator. WEITH (Unocal Corporation): Flue gas opacity can be from catalyst fines or SO3 in the flue gas. poor aeration and catalyst circulation could be causing pressure imbalances where you could have surging or fluctuating opacity problems. I called Mr. This unit retains an average particle size of 50 to 55 micron. ranges of commercial fresh catalyst properties. makeup amount. Parker’s remarks on catalyst resistivity. You probably want to check velocities of the primary and secondary cyclones to make sure they are in the proper ranges.4 to 1. but may be related to pockets of catalyst that get swept into the flue gas at higher velocities. which is why most refiners also use NH3 in the ESP (to lower the resistivity to the optimum level). As a matter of fact. We deal in equilibrium catalysts. On the precipitators we operate. Operation at low excess oxygen levels will minimize SO3 formation. you have a reduced free board and you might be overloading the cyclones. DELBERT F. We have the ability to inject sodium bicarbonate solid into the flue gas ahead of the wet gas scrubber for SO3 control. Therefore. We have observed that increased CO will actually help the corona current. There is actually a narrow range in which you can vary catalyst resistivity. rather they had a third stage separator. on some of our precipitators. so I called the refinery and asked if they recycled fines. If it is too low. if needed. for the U. apparently that affects the resistivity of the flue gas.79 to 0. McClung (from Engelhard) calculated the impact on opacity of density and attrition indexes as follows: Relative % Change in Opacity ABD CBD EAI -9 -6 +34 Range of Data 0.flue gas properties. the lower the attrition resistance of a catalyst. and we see a lot of catalyst analyses. SOLIS: I basically agree with what has been said. We have injected NH3 into the inlet of the electrostatic precipitators at a concentration of approximately 10 ppm to try to increase the efficiency of the precipitator operation. it is not always practical to do so. JAMES D. the higher the propensity to produce fine particles that increase opacity. DEADY: Our most dramatic change in flue gas opacity occurred when we shut the unit down and water washed the inside of the catalyst hoppers. If the level is too high. This seems to help somewhat. considering only operating aspects. The following chart provides particle size data from this unit over the last 8 years. We have reduced the flue gas velocity by minimizing the excess O2.S. 54 Heavy Oil Processing . We have found that maintaining control of the regenerator level and underflow system is needed to prevent fines carryover. which affects the efficiency of the precipitator. attrition index has the largest impact on opaciry. They have no problem with stack opacity at all. Most catalysts used today have higher resistivity than the actual ideal level for precipitators. deposits on the flue gas expander. This was somewhat effective but not dramatically so. TOLEN (Rocky Mountain Salvage & Equipment): We have tried a number of ways to improve the performance of our electrostatic precipitators. particle size distribution.91 to 0. Catalyst quality. I want to add to Mr. and catalyst density effects on the opacity measurement. opacity is clearly a function of FCC catalyst physical properties. Poor wet gas compressor control could also create pressure imbalances which would have the same effect. and catalyst velocity in the process are key factors to control fines production.1 Clearly.G. The hoppers were almost full of catalyst with only small openings to the dump valves. we do not necessarily see the same magnitude of change with the same adjustments. They hauled it out about once every 3 weeks. We have tried to reduce the visible SO3 particulate by adding SOx reducing additive — again with limited results. They lose almost no catalyst. I could not figure that out. and potential stack gas opacity. lowering the excess oxygen will also help.

92 .88 .86 .27 .92 .92 .28 . for several years now Mr.91 .90 5 3 2 3 1 2 3 1 1 3 3 2 2 3 0 4 2 3 2 2 3 0 1 1 2 4 2 1 2 2 0 3 0 3 2 28 31 31 28 25 22 25 25 22 23 22 24 25 26 24 26 25 24 25 22 22 19 21 17 19 16 14 15 18 18 17 16 15 14 17 84 89 89 83 81 77 81 81 82 80 76 78 81 81 80 76 80 81 85 80 71 75 78 78 77 75 72 70 76 75 79 73 75 68 75 54 52 52 55 56 60 58 57 59 59 59 59 57 56 58 58 56 55 56 60 61 62 60 62 61 64 65 65 61 62 62 64 63 67 63 09/05/91 09/11/91 09/18/91 11/13/91 11/20/91 11/27/91 12/04/91 12/12/91 12/19/91 01/01/92 01/08/92 01/22/92 01/29/92 02/08/92 02/05/92 02/09/92 02/13/92 02/17/92 02/19/92 02/23/92 03/01/92 03/06/92 03/08/92 03/27/92 04/01/92 04/08/92 04/10/92 04/14/92 04/23/92 04/29/92 05/05/92 05/19/92 01/05/94 01/11/94 01/20/94 01/25/94 02/04/94 02/09/94 02/09/94 03/02/94 03/02/94 04/05/94 04/12/94 04/20/94 04/27/94 05/03/94 05/10/94 05/19/94 05/25/94 05/31/94 06/09/94 06/16/94 06/22/94 06/29/94 07/07/94 07/14/94 07/20/94 07/27/94 08/03/94 08/10/94 08/16/94 08/23/94 08/31/94 09/05/94 09/14/94 09/21/94 09/28/94 10/05/94 10/11/94 10/18/94 10/25/94 11/02/94 11/09/94 11/17/94 11/22/94 EDWIN D.88 .30 .90 .26 .28 .92 .28 .27 .29 .29 .88 .88 .91 .86 .28 .87 .29 .26 .29 .28 .28 .89 .26 .91 .28 .25 .87 .30 .93 .27 .88 .92 . TENNEY (GE Environmental Services): Yes.27 .27 .29 .30 .31 .28 .95 .89 .88 .28 .26 .89 .91 .27 .27 .31 .27 .86 .86 .89 .27 .26 .91 .31 . We can assure you that most of the specifications for these cyclones were given to us by the process licenser and they are the same 1995 NPRA Q&A Session on Refining and Petrochemical Technology 55 .25 .92 .87 .93 .89 .91 .88 .91 .30 .27 .90 .92 .88 .29 .26 .29 .90 .90 .90 .92 .87 .91 .27 .87 .30 .99 .29 .91 .86 .30 .88 .88 .91 .29 .90 .92 .28 . Tolen has been accusing us of designing special cyclones for one refiner and not offering them to any other refiner.27 .30 .27 .91 .27 .27 .Sample Date Equilibrium Fluid Catalyst Analyses Particle Size Physical (microns) Properties ABD 0-20 0-40 0-80 AVG A PV m2/gm m3/gm gmm/cc 102 102 101 102 112 106 105 106 108 110 109 116 110 111 113 114 114 110 112 115 119 116 118 118 119 115 116 115 112 113 114 112 115 116 127 124 124 128 125 127 126 122 .31 .30 .87 2 3 3 4 2 2 3 2 4 5 6 7 3 6 6 5 4 4 2 2 4 4 5 4 3 2 2 4 3 5 5 5 4 3 2 3 0 1 2 3 3 4 22 24 28 28 25 24 27 26 27 29 31 35 28 29 29 28 30 29 28 27 27 25 24 23 26 26 25 28 24 29 26 26 29 29 31 32 32 28 27 28 28 31 75 79 77 78 79 77 82 75 80 81 82 87 82 83 83 82 76 80 77 76 80 77 78 72 72 74 74 78 75 80 73 73 77 78 87 86 82 85 80 83 83 84 60 58 59 59 57 58 56 58 57 55 54 51 56 55 55 55 55 55 56 57 58 58 58 61 57 58 59 56 61 55 59 58 58 56 53 52 53 55 55 55 55 53 Sample Date Equilibrium Fluid Catalyst Analyses Physical Particle Size (microns) Properties A PV ABD 0-20 0-40 0-80 AVG m2/gm m3/gm gm/cc 126 109 110 112 118 117 109 116 117 122 127 127 130 123 126 123 124 125 125 138 124 129 127 130 131 136 135 133 131 129 130 130 128 132 128 .25 .28 .87 .28 .27 .91 .89 .29 .91 .88 .89 .27 .88 .29 .29 .90 .92 .28 .26 .93 .91 .30 .91 .92 .30 .27 .31 .27 .28 .27 .27 .25 .28 .91 .90 .88 .86 .30 .29 .87 .87 .87 .26 .

As the overall heat transfer coefficient of a small diameter tube will be higher as compared to that of a large pipe. thus. Conventional cyclone systems (large diameter types). The old truism — garbage in. The mathematical basis is the fundamental Euler equations. Our TSS is Shell type and employs the conventional “reverse-flow” cyclone principle. The other type of separator consists of 6 to 20 larger diameter cyclones (±40” I. We have completely opened those bottoms to allow easier catalyst fine drainage. it is very important to realize that design parameters utilized should be in tune with reality. in general. because it is easier to put together the way it was rather than the correct way. Because of the small number ofcyclones and because these cyclones can have diplegs with valves. W. A perfect example is the changing operating conditions of internal cyclones inside the reactor/regenerator vessels. WEITH (Unocal Corporation): I think we all should keep reminding ourselves that a third stage cyclone is a true and typical mass transfer device. Rick Miller of M. There are 50 or more of these cyclones in the separator vessel. the third stage separator. One type has a large number of small diameter 56 Heavy Oil Processing . If they continue to increase throughput. a third stage cyclone having only a small number of large Based on conversations with Mr. However. In a sense. in all likelihood. recently they have increased throughput. we expect their catalyst analyses will be similar to those generally found in the industry. One will find that these separators protect expander turbines because they grind up the enter particles to less than 10 microns. can drop quite drastically as a result. The particulate level downstream TSS must not exceed 100 100mg/Nm3. as minor operational instabilities usually can be corrected at a later time with relatively little effort. The efficiency about doubled. All cyclones are typical mass transfer devices. The particle size analysis of the catalyst escaping from each type of separator is about the same. QUESTION 11. As a consequence we have also revamped and upgraded the third stage separator (TSS). there are two types of third stage cyclone separators.specifications that we have used for about 80% of the currently operating units. not everything may be lost at this stage. the fractional collection efficiencies of small diameter cyclones will be considerably higher as compared to those of large diameter cyclones. it appears they have not been pushing the unit. but the overall efficiency of this type of separator is only 40% to 50%. the principal design operants of cyclones may be compared to those of tubular heat exchangers. The unit was shut down to plug some tubes in the flue gas steam generator. and I discovered the nozzle was indeed in backwards. Their vortex stability is a function of their relatively large body geometry and volumetric flow of the continuum. We have installed a catalyst cooler and have increased by 20% the air flow to the regenerator.e. but the losses from the second type of separator are significantly less. react very unfavorably to changing operating conditions (turndowns). What upgrades are available to improve performance of existing third stage flue gas separators? SOLIS: cyclones (10” I. We have increased the number of swirl vane tubes by 22%.e. hence. We properly fitted the swirl assembly to keep it centered in the can to avoid cracks in the ceramic lining as it expands. TENNEY (GE Environmental Services): Basically. Their behavior (operational). both of which tend to minimize circulation of gases from one cyclone cone to another. is governed by the very same physical laws as those ofsimilar mass transfer devices. and their fines level and average particle size have increased. It makes an amazing improvement in efficiency if it is installed correctly. MANFRED DEHNE (Polutrol . Consequently. may not work properly as expected. they should closely correspond to and reflect operating conditions realized in the field later on. (They most often are the source of catastrophic catalyst surges occurring). Hence. i. Therefore..D. Our original TSS had swirl vane tubes that were closed on the bottom and had two slots for the collected fines to drain. If the initial design parameters specified are wrong. However. I was prompted to check the installation of our critical flow nozzle on the underflow of the third stage separator. Kellogg about two years ago. JAMES D. their efficiencies are inversely proportional to their diameters. i. Any plugging of these slots will cause the separator to not function properly. EDWIN D. This is compounded by the problem that it was installed intuitively. because substantial catalyst bypassing can occur if it is not. usually in a vessel. These items should be checked and maintained as required during turnaround to maintain proper performance. Their operating conditions are not unique..Europe): We have implemented an overall revamping of our FCCU at the Gibraltar refinery. Conventional cyclone separation efficiencies. We do not have an explanation for why this refiner has been able to retain the fines that they do. The seal weld between the swirl vane tube and top tube sheet was done very carefully to be airtight. garbage out — holds value for the design of third stage separators as well.D. Eff (small diameter cyclone) >> Eff (large diameter cyclone) In addition. this type of separator has a collection efficiency in the range of 75% to 80%. or less).). or what maintenance people thought was intuitively the right direction.

without compromise. can be made to operate quite stably. helical fashion inside a pressure vessel. The modular collector cells are interconnected via a grid-like construction. It achieves collection efficiencies of around 80 mg/Nm3 . having been carried our of the regenerator vessel). For orientation. and clusters ofsolids material (such as catalyst surges). I have made a few simple estimates of thermal conversion and yield at typical catalyst temperatures prior to feed injection. Final removal of the solids may be carried out by a typical underflow system. and E. it will not erode the inner liners and will not cut off diplegs as can be experienced often with old style. however. thus allowing free. Large size solids particles. VORTEX STABILIZER DEVICES are installed. they suffered performance loss. Has anyone used normal butane as lift gas or fluoridization medium in the base of the riser? What yield pattern changes were observed? ROSS: Although I am not aware of any direct experience with normal butane in the lift section of the riser prior to feed injection. these underflow rates should be about 3 wt % of the total flue gas coming in. where gases are discharged via CLEAN GAS OUT (H) upward and back into the main stream.and are temporarily collected inside the DEBRIS COLLECTION PLENUM (B). In addition. All modular collectors are installed in a quasi-horizontal. with UNDERFLOW and FOURTH STAGE COLLECTORS. into a separate FINES STORAGE VESSEL arranged underneath the THIRD STAGE VESSEL. by and large. Hence. If you go too high. As already mentioned. the THIRD STAGE COLLECTOR shown is subdivided into three distinct pressure chambers: A. Dust-laden gases enter the system at the upper inlet nozzle and are immediately expanded inside the FLUE GAS DISTRIBUTION PLENUM (A). uninhibited by thermal expansion. crying to push more gas to their expander and. So typically. of course. Still traveling at a very low velocity. e.already having been pre-sized and being of sufficiently small size . this particular third stage separator does away. I need to point out that the geometric axis of the cyclone structure and the axis of the vortex should not be confused. where the dust is removed via the SOLIDS FINES DISCHARGE (F). is very important. The diagram on page 58 shows a modern third stage cyclone requiring neither an UNDERFLOW System nor a FOURTH STAGE COLLECTOR. The position. the internal vortex finger will not jump to the wall when operating conditions change. This design minimizes the buildup of stresses. a gas-solids separation mechanism is triggered (via saltation). in order to promote stable operations over a wide range of operating conditions. QUESTION 12. STEVEN A. Solids material . But even a third stage cyclone with an assembly of a relatively low number of large diameter cyclones. Inside each modular collector cell. the flue gases are turned downward toward the horizontally arranged modular collectors (C).diameter cyclone tubes is more susceptible to operational instabilities as compared to one having a multiplicity of small diameter tubes. We have seen many instances of people cutting these rates down. it is possible to revamp/upgrade existing/older third stage cyclones to meet tougher emission standards. one of the other factors that will influence the performance or efficiency is the underflow flue gas flow rate. Each modular collector cell moves cleaned gases outward and toward the CLEAN GAS PLENUM (E). Correct positioning of the vortex stabilizers. Material collected there is discharged via the DEBRIS/ROUGH CUT DISCHARGE (G). standard type cyclones. In addition. debris (such as liner material. As a result. thermal cracking 1995 NPRA Q&A Session on Refining and Petrochemical Technology 57 . of course.will enter the modular collectors via their tangential inlet horns. The internal collector cells separate the solids particles from the gas stream and discharge them into the FINES COLLECTION PLENUM (D). is determined by the natural vortex procession. You can get re-entrainment or your cyclones will not be working very well. each internal cyclone is fitted with an internal vortex stabilizer device (patented). D. There. Each modular collector cell moves cleaned gases outward and toward the CLEAN GAS PLENUM (E). so-called modules. Via installation of vortex stabilizers. then you get re-entrainment. uninhibited radial and axial expansion of the internal system. where gases are discharged via CLEAN GAS OUT (H) upwardly and back into the main stream. You do not want any gas-to-wall impingement coming out of these tubes either. operations of the cyclone collectors will become stable and predictable. or by gravitational force only.g. That. which turns this modern third staged cyclone into a very stable operating device. A small size-large size solids particle disengagement process is initiated and promoted.W. inscalled. I think. On a final note. Kellogg Company): In regard to swirl vanes of third stage separators. continue on their downward path never entering the modular collectors . Their location is very important. KALOTA (The M. They are not identical. with a little bit of effort. These things function best when there is a certain downward velocity. a centrifugal force ofapproximately a hundred g’s is imparted upon each solids particle introduced into the system via the gas stream. the gas velocity is lowered to a level where solids back mixing is greatly minimized. It can be neither too high nor too low. Units rendering collection efficiencies of 50mg/Nm3 are already in service.. is related to the disengaging area underneath these swirl tube assemblies. For normal butane. As can be seen.

58 Heavy Oil Processing .

the steam stripper has remained out of service.completely without the influence of catalytic effects (which is a very simple chemistry to anticipate) at 1300°F to 1350°F and residence times on the order of 1/2 second to 1 second. What has been recent experience with improved riser termination devices for reducing contact time and thermal cracking? What operational Changes were implemented to maintain conversion levels? 1995 NPRA Q&A Session on Refining and Petrochemical Technology 59 . there is commercial precedent for excessive catalyst deactivation when stripping with steam at high temperature. The yields from the converted butane were 1 wt% hydrogen. The first was from the amount of CO and CO2 measured in the absorber offgas stream. 45% ethylene. Butane conversion was 40%. including hopper and standpipe. The differences between our product distribution and Mr. 2 wt% propane. or was this a question of getting amine consumption down in their treating section? I think the answer is not to mess with aeration rates and catalyst circulation stability for the sake of a little amine consumption. In the operating story. however. all the aeration air orifice plates. 8 wt% butylenes. In many cases. and catalyst skeletal density to correlate with the amount of gas entrained. you are going to have a certain amount of entrainment of inerts. it is a very bad idea to use butane as a lift gas as there is a lot of dry gas production. This allowed them to control accurately individual aeration rates so that the pressure profile would be as close to optimal as possible. We injected butane into a 1200°F laboratory FCC riser reactor with a 2-second residence time. KALOTA (The M. The flue gas and inerts will be effectively removed. this can be changed to steam. this entrainment. with the same caveat as above. ERNEST L. but never eliminate. Were they really just interested in reducing inerts to the reactor. which fed off of a single header to the standpipe. Have any refiners made mechanical or operating changes to the regenerator to reduce the gas environment to the reactor system? Can the reduction be quantified? DEADY: The key to success is the proper design of the catalyst withdrawal system. I am not sure if they quantified the amount of reduction in the gas entrainment they observed while the steam stripper was in service. 9 wt% ethane. In order to operate in this manner. Needless to say. replace them with steam or fuel gas. however. QUESTION 13. In the standpipe. Good standpipe design can help minimize. or even fuel gas. as this will result in excessive deaeration. one refiner modified the aeration rates on the regenerator standpipe such that they operated between 90% and 115% of theoretical. The hopper cannot be too large. depending on the partial pressure in the system at the time. Kellogg Company): I have two stories on this. LEUENBERGER (ARC0 Products Company): reduce the flue gas entrainment back to the reactor. aeration is typically accomplished with air. In that technology is a mechanism by which we can remove the inerts from the regenerated catalyst before it enters the reactor. One would expect the pyrolysis yield of the converted butane to be on the order of 2% hydrogen. We have a new technology under development called the X design. ROSS: I have some laboratory data that support Mr. were replaced with individual aeration tap flow meters fed from a series of pressure-controlled headers. a unit has been expanded or the capacity simply increased without modifying the catalyst withdrawal system.W. and the rest C4S and C5S. Obviously. 20% propylene. The second was by a proprietary design correlation that used catalyst circulation rate. Although tempting. compared to their previous operation where they were running about 130% to 140% of theoretical. Using this strategy they were able to accurately change aeration flows and patterns as the feed rates changed and as the catalyst circulation rates were varied in order to reduce entrainment back to the reactor. one operating and one mechanical. The mechanical story is of one refiner who installed a steam stripper for the regenerated catalyst in order to This question was kind of interesting because I wondered what they were driving at. we do have a potential solution in the works today. conversion levels from 20% to 60% can be anticipated. 18 wt% methane. MARK SCHNAITH (UOP): Unfortunately. However. The amount of air actually transported to the reactor could be quantified in two ways. 15% methane. steam stripping of the catalyst leaving the regenerator is not a good idea. Ross’s can be attributed to the hydrogen transfer activity of the FCC catalyst. STEVEN A. The catalyst must enter the withdrawal system at a velocity lower than the bubble rise velocity to allow the catalyst to degas. catalyst flowing density. 36 wt% propylene. 1 wt% isobutane. One other note concerning other sources of inerts in the reactor. 24 wt% ethylene. Ross’s calculations. When they turned the steam stripper off. and 1 wt% coke. QUESTION 14. if you have air purged instruments in the reactor. if you want to maintain good catalyst circulation. they saw an increase of about ten numbers in ECAT microactivity.

we conducted a radioactive tracer study to evaluate the performance of the equipment. a proper catalyst selection is essential to get the benefits of the new technology. as you would expect for less overcracking. an external cracking riser. We realized a dramatic reduction in the coke make on the unit and some reduction in the dry gas make. the gasoline yield may actually remain about the same even though overcracking would be expected at higher reactor temperature. etc. then by increasing the slurry recycle. One thing we found that seems to be significant is we are getting a higher product carrydown in the rough-cut diplegs than we expected. The refiner then adjusts operating parameters to take advantage of the wet gas compressor capacity to drive the unit back to its limit. the product vapors are quenched after the catalyst has been removed or separated in a RTD. We have recently revamped both catalytic crackers at that facility. Prior to the revamp. Examples of these RTDs include closed or close coupled cyclones.. In this system. However. We installed radial feed nozzles. I have to say that the results have identified substantial performance differences between them. The total cost of the revamp for the riser termination plus the feed nozzle arrangement was about $2. or maybe slightly better. the reactor temperature. or a combination ofall three. which requires no special operating procedures. Following the start-up. VAN IDERSTINE: Consumers Co-op has a 20. I will try to set the premise for some of the direct experience some of the other refiners on the panel may have.000 bbl/d UOP stack model FCCU. The gasoline to heavy cycle oil yield is up approximately 3% to 4%. these changes have improved our yields. Start-up and operability factors are important aspects of these systems. We have conducted extensive pilot plant work for catalyst screening. This results in cooling the product vapors by 50°F to 70°F without causing downstream coking as has been demonstrated in a three-year coke-free run on a 2% to 3% Conradson carbon feed quench with product to about 950°F Thermal cracking is 60 effectively terminated in a low-cost. Another technology that reduces post-riser product degradation is the Amoco post-riser quench licensed by Stone & Webster. catalyst activity. From our instrumentation. covering seven different catalysts. The most effective is an increase in catalyst-to-oil ratio which also results in an increase in yield selectivity. and in a third instance. we have seen yield changes that have been as expected. PARKER: I am going to relate a recent experience from our Borger. There are several modern end of riser separation or riser termination devices (RTDs) that improve both catalyst and vapor separation efficiency to avoid post-riser product degradation. vortex separator.ROSS: I hope you will bear with me. Our slurry make increased slightly. we had a standard elephant trunk termination off the riser. with the majority of that improvement occurring between the gasoline and the light cycle. the amount of improvement is dependent on the type of separator replaced. and the amount of postriser residence time eliminated. Typically 5% to 7% recycle of LCO (or similar refractory material) is injected just after vapor separation from the bulk of the catalyst. and external rough-cut cyclones. In one case. Texas refinery. Typical post-riser conversions of 4% to 5% are common with a residence time of about 20 seconds. In one case. was a reduction in regenerator temperature of about 50°F. The first unit is an old Sinclair side-by-side cracker. originally built in 1953. at the same time. These systems provide very high catalyst separation efficiency and deliver the product vapors from the outlet of the riser to the outlet of the reactor vessel in roughly five seconds. This summer we revamped the reactor with the UOP vortex separation device for riser termination and. Combined. both catalytic and thermal. In some instances. usually by increasing the riser temperature and reaping the benefits of higher LPG olefins and gasoline octane. We can increase slurry recycle because we are not at the maximum capacity on the FCCU. an increase in feed rate of about l0%. The LPG make is reduced by about 5%. Since start-up. as much as 10% post-riser conversion was measured resulting from a residence time of about 40 seconds. One of the side benefits we realized as a result of not overcracking and less delta coke. mechanically simple system. in another a drop of about 20%. The “lost” conversion when eliminating post-riser thermal conversion can be compensated for by increased catalyst-to-oil ratio. The industry is now well aware of the detrimental effects of post-riser cracking and product degradation. installed the UOP Optimix elevated radial feed nozzle arrangement. Gas make is down 25% to 30% for similar conditions. When installing an advanced RTD. made possible by the reduction in dry gas. Heavy Oil Processing . and for the feed we had a UOP premix-type nozzle at the bottom of the Y piece. The improved performance noted after installing an RTD is a drop in dry gas production and an increase in valuable liquid products. SOLIS: In November the reactor of our Huelva Refinery Exxon FCCUs will be revamped to be retrofitted to Exxon short contact time technology. As a consequence.5 million. and the Ramshorn Axial Cyclone licensed by Stone & Webster. we more than offset the initial increased slurry make. we observed a drop in dry gas of more than 30%. riser temperature. The payout should be within two years.

As expected. Abraham’s comments concerning the catalyst. one a 1950 vintage. Rare earth levels increased an average of 7%. Dry gas. coke. higher oleficinity from less hydrogen transfer reactions at the low contact time. HANSEN: We installed a close coupled cyclone system in October 1994.4 wt % to 1.we believe the diplegs are sealed. quantify your mechanical changes. Valero. and diolefin production have been reduced. Ms. JOHNS: Texaco has installed their negative pressure DirectCoupled Cyclone design at three locations: Port Arthur. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 61 . most refiners increased equilibrium microactiviry rare earth level on the catalyst and total surface area to maintain conversion levels. this same unit was revamped to include a closed cyclone system. If you think you will be able to address the severity loss with increased reactor temperature and catalyst-to-oil ratio. Texas refinery. 1010°F up to 1040°F and higher matrix catalyst activity. and Nerefeco. It has three internal risers. from 70 MAT to 73 MAT The unit was revised to allow higher catalyst circulation to stay in heat balance. We went to higher riser temperatures. As further testimony to the old saying there is more than one way to skin a cat. There are basically two schools of thought on that. At the Lake Charles. In general. our preliminary work suggests that catalyst activity is probably preferred. The other unit is a Kellogg Model C cracker. They have been modified several times over the years and currently have dual sloped risers and a combination of either inverted can or vented hood termination devices. So we are continuing to evaluate the cyclone performance in that area. Of all the operating changes that could be made. I guess that is self-explanatory. The catalyst flows through the plug valves up through the riser. and that the best yields are obtained if this is achieved with selective matrix activity. FRONDORF: One of our plants’ experience with riser termination devices began in 1987 when rough-cut cyclones were installed. And the range of the total surface area increase was between 10 meters squared per gram and 40 meters squared per gram. one in each of our refineries. before the revamp or after the revamp. and substantially lower delta coke resulting in lower regenerator temperature (30°F to 40°F). In 1995.000 bbl/d and 90. or who are constrained in raising their reactor temperature. we have two UOP catalytic crackers. this year we are revamping three FCCUs. increasing catalyst activity by 2 to 4 MAT numbers and increasing riser temperature were needed to maintain conversion. with external rough cut cyclones. revamped stacked unit. This allowed operating at slightly higher riser outlet temperatures and slightly more catalyst activity to replace thermal cracking with catalytic cracking. The last one in 1987 involved an elephant trunk design. We typically operated at maximum catalyst-tooil ratio and found that in addition to this. and we are using three different designs. would probably be better off adding the more active catalyst before the revamp. The current plan on that unit would be to increase catalyst activity to maintain conversion levels following the completion of the revamp. depending on which FCCU we are discussing. which further reduced thermal cracking as evidenced by lower coke and dry gas production. That particular unit has plug valves inside the regenerator. The first unit is due to have its turnaround and revamp in the spring of next year. we have three 1944 vintage Kellogg Model 2 catalytic crackers. DEADY: I want to add to Mr. We have not made any recent changes to riser termination at the Corpus Christi plant. That unit appears to be performing very well.000 bbl/d capacity. and then switch to the more active catalyst. microactivity numbers increased by a range of 3 to 10 with the average being about 5 numbers. We have not done tracer studies to determine the residence time or the separation efficiency. with a range of 0. We installed nozzles on the plug valves using patented technology from Amoco and installed inertial separators on the end of the risers. ABRAHAMS: around catalyst. Results from all three locations demonstrate significant reduction in dry gas make. Conversion level was maintained in all cases by increasing catalyst circulation and increasing the rare earth content of the catalyst to provide higher activity. We are initiating another set of revamps to move to full vertical risers.1 wt % rare earth on the catalyst. A refiner recently asked us when refiners are going to these more active catalysts. All of them are between 70. the expectations for improved termination would be higher reactor temperature and/or catalyst activity to maintain the same conversion level. then you can probably start up on the pre-turn- At our Corpus Christi. we went from 55 to 68 tons a minute. Specifically. Deady was exactly correct because the team has already sat down with the catalyst vendor to lay out a plan on how we want to handle catalyst activity at the time of the revamp start-up. the other a 1975 vintage side-by-side. Refiners concerned that they might not be able to circulate enough catalyst. We have surveyed several refineries who did these types of revamps to determine the shifts they made in catalysts. Louisiana refinery.

We tried to correlate that in our own plant because we run significant levels of basic nitrogen. First of all. PAUL SESTILI (The M. we will be conducting a commercial evaluation of a low NOx combustion promoter that has shown promise in the laboratory. Refiners have the ability to reduce NOx 62 We have commercial experience in several units using a low NOx promoter. Kellogg Company): Not to belabor the point. Moving to a partial burn operation can help. You can also look at reducing the nitrogen in the feed by FCC feed hydrotreating. it will show up as NOx on some of the stack tests. SMITH (Exxon Research & Engineering Company): Recent experiences with short contact time designs for both grassroots and revamps have met or exceeded expectations for both yields and operability. Excluding the effects of SOx reducing additives. The most effective method ofcontrol is operation at lower excess oxygen levels. and we could not correlate with the stack NOx. The panel has already mentioned these factors. but produces about 30% less NOx. To give you a quick summary of our recent experience. is converted to NO2 using sodium chlorite. QUESTION 15. a high dipleg vapor carryunder was detected with a positive pressure cyclone. despite sealing the dipleg in the stripper bed. G.W. Again. we are expecting a commercial trial of this material by the end of the year. As contact time and therefore thermal cracking are reduced. catalyst-to-oil ratio. Improving catalyst air distribution will also help with your NOx. and we expect to have a trial of this material by the end of the year. They include catalyst activity. other factors must be adjusted to maintain conversion and achieve optimum yield selectivities. is a drop in regenerator temperature of 25°F to 30°F. HANSEN: Our operating permit limits the amount of NOx in the flue gas. Afterburn can be a problem. During stack testing. what are refiners’ experiences with NOx reduction from the FCC regenerator? Has afterburn become a problem? DEADY: from the FCC regenerator in a variety of ways. We know one refiner. increased conversion. The NO2 is then absorbed. especially at lower flue gas rates. Our riser termination device. whereas we agree that the riser termination device is important. In addition. as Mr. Inc. It is interesting to note that in the Phillips Borger radiotracer study.5%. We are investigating. about 100 years of cumulative operating experience. and careful use of platinum-based combustion promoter. what tends to happen relative to a positive pressure cyclone system. and reduced dry gas production. catalyst formulation. and this has been clearly demonstrated by the observation of these substantial decreases in regenerator temperatures. This will in turn lead to higher hydrocarbon carryover rates to the regenerator. PARKER: There have been reports in the literature on a correlation between basic nitrogen in the feed. and eliminated a brown NOx plume. we think the operating characteristics of the riser termination device are equally important. additional additives that will reduce NOx by promoting the reaction between the NO and reductants such as CO or coke. A separate quench circuit is needed for this process because of the chemistry differences between NOx and SOx removals. So. which produces higher catalyst-to-oil ratios. which is typically the dominant species in NOx and insoluble in water. In a paper presented at the 1994 meeting of the Japan Petroleum Institute. and about a million barrels a day in current operation. When we actually look at the performance of the commercial units. such as 0. Managing promoter additions is also a key way to control the NOx. is a negative pressure cyclone system that minimizes hydrocarbon carryover to the regenerator. who decreased his excess O2 from 6% to 2%. It is widely accepted that excess addition of standard CO promoters can increase FCC NOx emissions. in conjunction with a major oil company. ANDREW SMITH (INTERCAT Inc. Johns pointed out. since increasing feed nitrogen has been correlated with increasing NOx emissions. Laboratory testing shows reductions of about 40% to 50% of NOx.) Some of this question was also covered last year in the 1994 transcript. but as you all know Kellogg offers Mobil closed cyclones as our improved riser termination device. we did discover that if you have any ammonia or cyanide compounds in the flue gas from a quench or anything like that. we have 19 units in operation that have been successfully running since 1985. However.GEORGE A. There is a wet DeNOx process available. In this process the NO. ROBERT GLENDINNING (ABB Lumus Global. Yields have been excellent and operations have been very robust over quite a wide range of operations. an extreme case. We have found that a combination Heavy Oil Processing . sometimes the NOx from the CO boiler could still be a problem. Lummus currently licenses FCC technology with Texaco. in the 500 ppm to 1000 ppm range. and operating temperatures. we outlined the advantages of negative pressure direct coupled cyclones relative to positive pressure systems. lower the excess O2.): For anyone in the audience who may not be aware. This new combustion promoter has activity for CO combustion similar to that of conventional production promoters. and NOx. and we agree.

These are correlations of data from Mobil FCC units for three different types of regenerators.of a low-platinum promoter added at a constant platinum rate reduces NOx emissions and avoids afterburning. KING YEN YUNG (Akzo Nobel Chemicals BV): My answer is in regard to the previous question about NOx reduction. are going to show the best NOx performance. some 20°C. In Europe. we have an application that was using additive and they were suffering from afterburn. which is a side entry dense bed regenerator. and on the bottom axis you have the percent oxygen in the flue gas. In a more recent example. The following chart shows the percent of the nitrogen in the coke that goes to NOx on the left side. a refinery reduced the promoter addition by 40% and could reduce NOx by 50%. One of the reactions that occur in a regenerator is that the NOx initially formed can react with the carbon in the regenerator bed and be converted into nitrogen gas. In the countercurrent regeneration process offered by Kellogg. and the lower curve is from the Kellogg Countercurrent Regenerator. units with good catalyst and air distribution. The curve in the center is a combustor type regenerator. They switched to a more effective promotion catalyst (INSITUPRO option). which can run at low excess oxygen with little or no combustion promoter. With this more effective promoter. You can see from the chart that the countercurrent regenerator provides a much lower percentage of the nitrogen in the coke going to NOx. PHILLIP NICCUM (The M. I agree that a good way to achieve NOx reduction is through promoter management. they reduced the platinum on ECAT by 70%. Kellogg Company): Given the effect of combustion promoter and excess oxygen on NOx. so there is a greater opportunity for the NOx to be reduced to nitrogen. Recent publications by W. the spent catalyst is introduced evenly over the top of the regenerator bed. with some of the nitrogen emerging as NOx. The top curve is the so-called swirl regenerator. In addition. W. it has been found that the NOx is the result of nitrogen in the feedstock. Grace indicate that most of the nitrogen in the coke is converted into nitrogen gas in the regenerator. The penalty was increased afterburn to 40°C. NOx from Commercial Regenerators 1995 NPRA Q&A Session on Refining and Petrochemical Technology 63 . R.

If the flue gas SOx level is less than 700 ppm to 900 ppm. especially on his point that the break-even point is highly unit-specific.decreased afterburn to 5°C and achieved a NOx reduction of 30%. the cost difference is about break-even. As an example. The Lake Charles refinery is in the process of installing an FCC feed hydrotreater and our plans at this time would be to continue the SOx additive on an as-needed basis. DEADY: Our Corpus Christi. uses SOx reduction additive on a regular basis to meet final stack specifications. we would recommend a commercial trial of SOx reducing additive just to quantify that performance. Again. We have not observed increased sulfur (or decreased sulfur. which lowers the SOx ppm about 20%. Based upon our experience. because of the new source performance standard requirements. Louisiana refinery. assuming a requirement to reduce it to less than 300 ppm. We see that the SOx reducing additives are most cost-effective if you have SOx emissions below 2500 ppm base. Issues to be addressed include the following: Required reduction in SOx emissions Capital cost Operating and maintenance cost Heavy Oil Processing . which is effective in reducing the emissions to below our limit of 99 ppm. We have no plans at this time to install a flue gas scrubber. If the SOx level is higher than that. How do refiners determine which technology to use? When using the catalyst additive approach are there any significant shifts in sulfur content of the various liquid products? SOLIS: scrubber scenario. Several SO x reduction technologies are available to the refiner (catalyst additives. Neither refinery has seen a significant shift in sulfur content of the liquid products following SOx additive. We found that it is unit-specific because the SOx capture efficiency of SOx reducing additives such as DeSox™ is extremely unitspecific. Based on feedback from our customers for the 64 I understand there is a broad difference of opinion on the breakpoint between the SOx level and when the catalyst additives are useful. but we have observed that some SOx catalyst additives can slightly reduce the sulfur in the FCC naphtha. we have seen trials measuring an effectiveness of 50% to 70% in the first stage partial combustion regenerator of a twostage regeneration resid unit.000 bbl/d unit. with an additional capital cost of about $50. the operating cost would be about $9. The standards with the flue gas scrubber are a little different. However. so it should be reviewed on a case-bycase basis. the lower operating cost of the scrubber will easily offset the higher initial capital investment. All the sulfur recovered from the flue gas leaves the unit as H2S. for that matter) in any of the liquid products with the SOx additive approach. Regarding the second part of the question. Texas refinery. which would not be necessary with the scrubber. KELLER: We are currently using an SOx reducing additive. operating on hydrotreated feed. In some of the analyses we have done. The scrubber investment is used as a credit for the electrostatic precipitator. QUESTION 16. We use SOx reduction additive on an as-needed basis to meet final stack specifications. does not have a flue gas scrubbing system. we see a slightly higher break-even point with DeSox™ technology. The catalyst additive has no significant effect on the sulfur distribution of the liquid products. We currently add a 40-lb dosage (110 ton catalyst inventory).000 a day for a typical 50. the sulfur that is removed is SOx from the regenerator and is converted to H2S in the reactor. or less than 50 ppm SO2 emissions. A spot reading from the Lake Charles plant for our SOx additive reduction would be about 35 cents per pound of SO2 removed. additive efficiency and prices are highly variable. I feel that unless a scrubber is in place. For existing units. the cost for the additive approach to reduce SOx from about 600 ppm to about 300 ppm is about $4. scrubbers). Each SOx reduction technology has advantages and disadvantages which are site-specific. it should be realized that additives are not very active in partial combustion mode units. We have not seen any significant shifts in the sulfur content of the liquid products with the use of the additive. Regarding its effectiveness in partial combustion. catalyst additives are the convenient solution. In general. operating on nonhydrotreated feed. FRONDORF: Selection of flue gas sulfur control technology is driven by the cost of the wet gas scrubber and the cost of the SOx additive. Above about 3000 ppm base SOx. it suggested somewhat less than 1500 ppm and perhaps closer to the 1000 number we heard before. ROSS: I agree with Mr. and cost-effectiveness tests in pilot plants are recommended. The Lake Charles.000 for a loading system. Solis. This is in order to achieve the new source performance standard requirement of 90% SO2 emissions reduction.000 a day with a capital cost ofabout $20 million. Local economics may shift the break-even point. This reduction typically lasts from 4 to 16 hours. because this is so unit-specific. the flue gas scrubbing economics can become much more attractive.

an overall analysis of the benefits of each system must be made. reduction catalyst plus electrostatic precipitator. CITARELLA (Exxon Research & Engineering Company): We also agree with the remarks that have been made regarding the fact that SOx control technologies are sitespecific and depend on the costs and benefits of the various alternatives. but lower maintenance costs and operator attention. The catalyst plus precipitator option has a lower capital cost.Compatibility with FCC process & ability to cope with catalyst fines Adaptability for dealing with other pollutants such as NOx and particulates Discharge issues — water discharge. VICENTE A. The wet gas scrubber tends to have a higher capital investment.): With the recent improvements in SOx additives. Kellogg Company): Kellogg Comparison Of Pollution Control Options To determine the most applicable technology for pollution control in a refinery. to determine their economics. Our wet gas scrubbers can achieve SOx removal in excess of 90% and meet SOx 1995 NPRA Q&A Session on Refining and Petrochemical Technology 65 . like the NO-SOx family. or purchasing ones with 40% greater pickup efficiencies at similar pricing. In summary. G. such as the Exxon Wet Gas Scrubber System. the purge treatment unit can be placed off-site. See following table. the on-site plot space requirement is much lower for the scrubber. W. It is my opinion that the economics will continue to favor the SO x additives over mechanical scrubbers for years to come in many cases. whereas the ESP waste is a solid dust only. opacity Plot space requirements PAUL SESTILI (The M. however. ANDREW SMITH (INTERCAT Inc. As a result. refineries have a choice of purchasing an additive with equivalent performance to current deSOx additives that cost 40% less. but requires more maintenance and operator attention due to the ESP. solids disposal. Kellogg recently completed a study comparing a wet gas scrubber to a SO. The only thing that I would like to add is that scrubbing. The waste disposal for the scrubber is both solid and liquid. it is important to look at the big picture when determining the most applicable pollution control system for a given refinery. The overall plot space requirement for the scrubber is higher. is really the only option that controls both SO x and particulates in one single unit. We would also advise refiners that are considering their options to run a short test with a SOx additive.

greatly favors the deSOx type operation. too. Again. if your scrubber has a malfunction. large batches of catalyst addition. CITARELLA (Exxon Research & Engineering Company): With respect to the need to shut down an FCCU because of a scrubber malfunction. and a review of the study’s content and decision process can be found in a paper compiled by Belco entitled Flue Gas Cleaning on Fluid Catalytic Cracking. ESPs are part of the operating permit where we live.S. we have a very long history (over 150 unit-years) of Exxon wet gas scrubbers in operation and have not had any situation where an FCCU has had to be shut down because of a wet gas scrubber malfunction. The spike of fresh catalyst activity can result in a short-term overcracking situation with an increase in coke and gas products. fully automated. Catalyst withdrawal is usually done on a batch basis since it does not change the composition of the ECAT inventory. WEITH (Unocal Corporation): I am aware of the IFP-Total design employed in two resid crackers and a system used by BP for continuous withdrawal and addition of catalyst. aged particles of catalyst in either continuous or non-continuous mode. where catalyst addition is quite large. process. you may find it necessary to shut down your FCCU. and can simultaneously meet the U. and economic variables play an important role as mentioned by several of the people.emissions standards for FCC feeds with up to 3% sulfur. or 50 mg per normal cubic meter. Continuous addition also levels out the catalyst loss associated with fresh addition to avoid peaks in catalyst loss. I suppose we were lucky at this. continuous addition and withdrawal almost become a necessity due to the large quantities ofcatalyst involved and the cyclic catalyst activity which would result with a single large batch addition. but there should be no difference if you are withdrawing from a location that preferentially removes the older. For residue cracking operations. at this time. continuous withdrawal is not required unless a special off-line catalyst demetalization process is considered where very large movements of catalyst out of and back into the unit are required. QUESTION 17. to me. I would further like to mention to those of you attending the NPRA Environmental Conference in two weeks in San Francisco that Belco and Valero Refinery will be presenting a paper entitled FCC Offgas Cleaning at the Valero Refinery in Cops Christi. completed a study in regard to catalyst additive and scrubber options for deSOx Obviously. These product increases can be seen in the main column and gas concentration facilities and the disturbances prevent continuous operation at the highest throughput. your operating permit requires that the scrubber be in service. In this case. Please contact Belco at the address below to obtain a copy of this paper. THOMAS WALKER (Belco Technologies Corporation): For this response I would like to relate an experience I had on a unit several years back. Generally speaking. this paper reviews Valero’s decision and operating experience with the Belco EDV. particulate removal specification of 1 lb per thousand pounds of coke burned. Both systems use conventional dilute phase withdrawal and injection systems with the IFP-Total system using a special flow regulation valve utilizing a ceramic lining for long life. but its purpose is mainly to cool the withdrawn catalyst so it can safely be sent to the storage hopper. Does anyone have a continuous catalyst withdrawal process? Do you see any benefits in doing this? There are operational stability benefits from using continuous catalyst addition rather than short. ROSS: Belco. we have to shut this system down periodically to make batch withdrawals. As long as the time for withdrawal is relatively short. This unit had continuous catalyst additions. which is frequently specified abroad. withdrawals are made on a daily basis. VICENTE A. In RCC units. For that reason. that refinery had opted for the Belco EDV scrubber. in association with a New Jersey refinery. and no process performance issues are seen. JAMES D. Continuous addition is considered best practice as the catalyst activity level is maintained at a nearly constant level. From an operating standpoint. MARK SCHNAITH (UOP): There is a large RCC unit in the Far East operating with a continuous catalyst withdrawal system. larger. We have moved from once-a-day to continuous FCC catalyst addition. Due to common lines. However. 66 Heavy Oil Processing . say 1 to 2 hours. there is a continuous withdrawal system. SOLIS: Regarding flue gas scrubbers being part of the operating permit. per Mr. many environmental. and we tried continuous withdrawal for several months with no noticeable effects. it is unlikely that an interruption in fresh catalyst addition will be seen. I would like to state that. MORGAN: JOHNS: Once a scrubber has been approved by a state. that. Morgan’s comment. Adedicated line is typically provided for this purpose and should not interfere with withdrawal operations.

the systems were plagued with poor operability and inability to adequately backflush the fine material from the pores of the filter media. ROSS: We currently operate a Gulftronics filtration system for our slurry. they have not tried these filters again. coker. We backflush the Gulftronic filters with heavy vacuum gas oil and send the backflush to our riser. We considered sending the backflush to our No. This system has been in operation for more than one year. which reduces catalyst content of the slurry from 0. one key is to have an effective cooling system to avoid overheating the storage hopper. One refiner notes that good equipment layout for access and quality valving for automatic backflush are vital components of a successful design and are not areas to try to cut corners or costs. Disposal is typically limited to the FCC riser. Periodically. We have had very few maintenance problems with the system to date. STEPHEN J. A very fine filter will simply recycle small particles resulting in an increase in the fines concentration in the oil as well as a very high pressure drop across the filter. As a contrast to what Mr. The first filter was located in the tank farm with 1995 NPRA Q&A Session on Refining and Petrochemical Technology 67 . Our suggestion for disposal of backflush in this situation is to send it to a coker if possible. The oil retained on the captured catalyst is recycled back to the riser with the backflush. The high rate is necessary to control metals levels on the equilibrium catalyst. The first filter was commissioned about 5 years ago and is not currently in service. As a result. A typical product oil stream will contain about 50 ppm catalyst or less. It gives you more fresh catalyst inventory and also gives you some flexibility in possibly blending a couple of catalysts. A cake of catalyst builds up. and we got rid of it. 6 fuel stream. Since then. the filter system was removed from service and moved to another location. maintenance was high. SIM ROMERO (BP Oil): We have two sintered metal filters in Ohio. The unit is not equipped with an electrostatic precipitator. YANIK (Akzo Nobel Chemicals Inc. The second filter has been in service for the last 3 years and is operating with little to no problems. if specifications allow. The backflush material was sent to the riser and caused opacity problems since the stack was the only place for fines to go. and a new unit about to start up will use the same system. One resid unit that I am aware of used the sintered mesh filtering system with excellent results over three years.that can operate at rates of 30 tons per day withdrawal. It has a couple of benefits. ABRAHAMS: One of our plants used a porous metal filtration system on its slurry oil. The backflush sequencing valves and recycle pump are the areas requiring attention as the fines content is high and care must be taken to maintain the equipment. In a system like this. and. Backflushing to the riser does create unique problems with control on your FCCU.): DEADY: I am aware of a couple of locations in the Asia-Pacific area where people have justified the use of a second fresh catalyst silo just to make sure that catalyst addition is not interrupted while they are pulling a vacuum to load from trucks or containers into the other silo. the cake must be removed by backflushing into the FCC riser to limit pressure drop. So. Bight now that is the best place that we have found to put the material. and all of those tested were unsatisfactory. as well as periodically backflushed. Have the etched disc or porous metal type fillration systems been used commercially in FCC slurry service? What are typical solids removal efficiencies and oil recoveries? What are the alternatives for disposing of the backflush material besides recycling back to the FCC riser? What are the maintenance histories? EMANUEL: I know a refiner who tried some of the porous metal filtration systems in their slurry system a couple of years ago. Control of the filter size/efficiency is important if the material is to be recycled to the riser. Efficiency is very good with virtual exclusion of particles greater than about 15 microns. While the removal rates were very good. but the content of the ash was too high and would have brought the fuel oil off specification. or asphalt. Another refiner we are aware of has experience with both the sintered mesh and filter systems. The key to the operations was the location of the filter. When a sintered metal filter is used without dependence on the cake. These difficulties made these systems extremely unpopular with the operations personnel. the elements must be periodically cleaned off-line. The selection of a 10 to 10 micron cut point recycles only that material which can be partially retained and eventually lost to the flue gas system. having two fresh catalyst silos is becoming rather common on those big residual cracking units. and that is a constant problem for us as far as cycling the unit is concerned.005% ash. we had a Gulftronics filtration system in one of our refineries. in addition.2% ash to a clarified slurry oil product with 0. A finer filtration will likely require disposal means other than recycle. Emanuel was saying a minute ago. forming on the filter with the cut point on particle size typically between 10 to 20 microns. QUESTION 18.

and in all cases the backwash fluid is designed to go back to the riser. In this case. We have seen refineries improve the propylene recovery through various methods. with lean oil pumped from the separation drum to the absorber. In particular. after installing the cryogenic unit. shut down the sponge oil absorber altogether. I do not have the efficiency gain numbers. But if you are looking for concentrations just under 500 ppm. The role of the absorption and stripping section is to remove C2. we handle this somewhat differently. they tend to build up in large quantities in the middle trays of the column. potentially a large quantity of methyl acetylene or propadiene could leave the column with either the overhead or bottom product. We believe it was successful. Ofconcern in propane/propylene splitters is the potential buildup of trace contaminants in the column. when present in trace quantities in the column feed. Because the gas and the oil contain moisture. The etched dish and Gulftronics are very good if you need to get a very low solids concentration. It limited the temperature on the top of the absorber to no lower than 60°F. The result showed increased propylene recovery from 81% to 89%. Texas. However. In this case the gas plant absorber was limited to 140 psi operating pressure. Rather. KALOTA (The M. BROWN (Pall Process Filtration Co. these components do not readily leave the column with the overhead or bottoms product. This filter had plugging problems and required frequent cleaning (about every 3 to 6 months).): Pall Rigimesh® backwash systems are now being commercially used in refineries throughout the world. What is the current technology available for improved C3= recovery? What are other refineries doing for C3= recovery? What is their normal recovery efficiency? SHEN: Propylene recovery depends heavily on the yield structure coming out of the reactor. Thus. have volatilities between those of propane and propylene. we had to watch hydrates formation. when the column is upset. QUESTION 19. The second approach is the addition of a cryogenic unit for the tail gas. The other eight are now in the design and construction stage. The typical influent for the solids is between 3000 ppm and 5000 ppm with the effluent consistently being below 50 ppm. there have been twelve systems sold. To date. but I do not know it. causing either stream to go off-specification. So it is difficult to compare one case to another because often they are not on the same yield basis. The filter has been in operation for 3 years and has been cleaned only once. The numbers we have in this case are from 81% to 90% recovery. there’are other alternatives: liquid cyclones or hydrocyclones made by Dorr Oliver or Vortoil. and our studies show that a higher pressure absorber tower is actually more economical than the cryogenic system. Propylene recovery from the Gas Concentration Unit is a concern. and then goes to a separation drum. methyl acetylene and propadiene. to 350°F — too cold. but the current recovery percent is in the mid-90s. SOLIS: In fairness to everybody who makes slurry separators. PARKER: At our Borger. the absorber tower runs about 260 psi and the propylene recovery is 92%. the presence of these components in the column does not affect column performance or product quality. and there are currently four in operation. The other filter was located at the unit and had a much hotter feed. The first is a combination of increased lean oil circulation and adding trays to the de-ethanizer absorber tower. We used refrigeration to cool the naphtha for the absorber and the lean oil for the sponge absorber. 68 We have a conventional absorption and stripping section and a high-efficiency fractionation system to recover and purify propylene. The oldest has been in operation for over 3 years with minimal maintenance problems. We also did a process study for a low pressure FCC gas plant. On our newest catalytic cracker at Sweeny. Texas refinery we replaced trays with packing in the top three trays and the bottom twelve trays in the lean oil absorber.feed at 300°F. Kellogg Company): The third case involves the high pressure absorber tower. The overhead vapor out of the lean oil absorber is combined with the lean oil prior to the lean oil cooler. COS. There is probably a name for this. ROBERT L. Downstream of this splitter we have a molecular sieve treater to remove the traces of COS. The hot feed reduced the plugging in the filter. Our Heavy Oil Processing . Question 1) to separate propane from propylene. The quantity or the volume of the backwash fluid is typically less than 2% of the amount of slurry oil that is being processed. One data point we had for a 175 psig absorber system showed an increase in the propylene recovery from 79% to 87%. then one of these liquid cyclones is a good alternative that is not quite as expensive or as maintenance-unfriendly. H2S and. We have a loss of 5% of propylene in the propane bottom stream. This is for a grassroots plant. Generally. W. At least one refinery we know of. STEVEN A. The fractionation system consists of a high performer propane-propylene splitter (see Petrochemical Processing Session. Our propylene recovery in this section is 93%.

feed vaporization. and see normal recovery efficiencies approaching 95%. Recoveries in the range of 92% to 95% can be considered current good performance. TOLEN (Rocky Mountain Salvage & Equip.5 and the riser 1995 NPRA Q&A Session on Refining and Petrochemical Technology 69 . The system is based on a typical lean oil design.6% of the C3s and almost all of the C4s out of the fuel gas. Once the existing process has been optimized. Inc. the major concern for these units is including sufficient flexibility to maintain recoveries over a reasonable operating yield range. we are beginning to look at a new process that uses ultra high pressure lean oil absorption. Improving yields from below 90% to this range is usually straightforward and includes maximized absorber pressure to the compressor limits. approximately GOOF. increasing the intercooler duties and increasing C2 s that might be allowed in the alkylation unit feed. Twenty-five years ago we built a refrigerated gas absorption plant in a 20. Inc. and main column overhead liquid is fed 10 trays down in our 40-tray primary absorber. We have a UOP Gas Concentration Unit. KELLER: Typical propylene recoveries from gas conservation units are from 92% to 95%. which has been in operation since 1987 processing FCC offgas with a simple payback of 11 months. but it is designed to operate at high pressures with a proprietary lean oil. Stand-alone refrigerated propylene recovery units have been used with varying degrees of success. An example of this type of system can be found at Mobil’s Beaumont. From what we have seen. which may include turbo expansion and/or refrigeration. and catalyst separation. with losses to the offgas system. There are several distinct zones in the FCC riser: catalyst/fied mixing.): Increased propylene production more than proportionally increases losses at any given concentration unit. to minimize the production of dry gas and achieve maximum conversion? ROSS: We currently recover about 92 wt % of the C3=. chilled intercoolers. upstream of a primary separation device. If ethylene recovery is also desired due to the proximity to a petrochemical complex. Sponge oil (typically LCO) has little effect on C3 recovery in the primary absorber unless C3 recovery is poor. QUESTION 20. which can be found in your FCC unit. The payout on that operation was about nine months. A more effective and economical approach than increased lean oil circulation is the addition of a cryogenic recovery system. We see a recovery efficiency of around 93% on that system. mixing. EMANUEL: reducing the absorption oil temperature. Absorber efficiency has little impact on C3 recovery unless the column is flooded. a selfrefluxing dephlegmator exchanger-based system should be considered. we operate with a primary absorber only with a chilled lean oil system. A common step to improve the efficiency is to chill the lean oil to about 50°F resulting in about a 95% to 97% recovery. We have seen recovery improvement anywhere from 3% to 5%. Any of these cryogenic systems will recover essentially all of the propylene. product vapor. The stripper (or de-ethanizer) performance can have a significant impact on recovery. DELBERT F. They principally depend on the pressure and how you run your stripper to strip the H2S. the process and equipment designs that should be looked at include chilled lean oil and main fractionator overhead liquid. with cooling water for heat removal. At constant conversion. This drum will use the cooled debutanized gasoline as the lean oil. Texas facility.000 bbl/d refinery to recover the propylene and butylene. similar to what has previously been mentioned. which uses a primary absorber to absorb 91. recoveries to 98%+ are possible within the unit. Debutanizer bottoms is the lean oil at the top. So. and vaporization are nearly ideal. presaturator. the catalyst circulation rate must increase from about 6 to 7.): In addition to cryogenic-type processes. ANDREW SLOLEY (Process Consulting Services Inc. FRONDORF: Our Corpus Christi refinery operates with a primary and a sponge absorber system. REZA SAOEGHBEIGI (RMS Engineering. the economics are very clear cut on installing refrigerated gas absorption.): Another option to improve the C3 /C4 recovery is to install a presaturated drum. and process control issues. With chilling and improved process designs. What is the preferred contact time between catalyst and oil. especially if the absorber is stacked on the stripper (no recycle to the high pressure receiver condenser). At the Lake Charles refinery. riser vapor phase catalytic cracking. Circulating pilot plant work has demonstrated significant gasoline yield and selectivity benefit when reducing the riser vapor phase catalytic cracking step under conditions where the initial contacting.recovery there runs about 3% propylene in the offgas during the summer months. The company currently marketing this process is Advanced Extraction Technologies. ROSS: A new lean oil system with sponge absorber will recover about 93% to 95% of the propylene.

Dave Bartholic of BAR-CO is pleased with Mr. which is currently in design and construction. the reaction rate is proportional to the contact time times the temperature. Kellogg Company): The optimum contact time between catalyst and oil in the riser depends on several factors: the type of feed being processed.5 to 2 seconds. At the M. and lower regenerator temperature. These results were obtained using conventional catalyst withdrawn from a commercial unit. eliminates the reactor riser and features an ultra short contact time while maintaining effective conversion. TOLEN (Rocky Mountain Salvage & Equipment Co. and is feedstock dependent.S. JOHNS: TUAN NGUYEN (The M. Just as the ethylene industry moved from simple mechanical layout designs to control residence time to quench fluid injection to freeze degradation reactions. VAN IDERSTINE: Historically.001 and 3. High conversion cannot be maintained in ultra short contact time cracking because there is a minimum residence time required for atomizing and vaporizing the feed. W. a very efficient feed injection and catalyst mixing/contacting system is required. ANDREWS (Consultant): I am sure Mr. DELBERT F. you are going to have to run the reactor at a higher temperature than you run the regenerator in order to get the reaction you want.4 seconds. Ross’s remark about 0. In June 1995. Another consideration of short residence time systems is that of product quench.5 seconds in the riser vapor phase cracking section. So. My observation of a unit with extremely short contact time was that once they reached a conversion level of about 78. the BAR-CO MSCC process. you can improve your yield selectivity dramatically.1 seconds and becomes a significant part of the total residence time. at the same conversion. we have seen little or no advantage for going to “ultra short contact time” cracking.3 second residence at 17. This is dependent on paraffin content and carbon residue in the charge. The optimum residence time for each refiner depends on what their hardware configuration is. and diffusion of the hydrocarbon products out of the catalyst. and therefore the catalyst was not an optimized formulation for short residence operation.): For the direct coupled system previously discussed. at Texaco we design for maximum conversion with minimum gas make and a contact time of 1. We are currently at a 2. New high-efficiency feed injection techniques combining efficient atomizing feed nozzles and novel injection orientation have demonstrated extremely rapid reduction in riser density after feed injection. Gamma scans of a commercial riser configured with new feed injection techniques demonstrated a density decrease from dense catalyst below feed injection to riser outlet density in about 1 meter. and some of the selectivity gains can be lost. Kellogg Technology Development Center. the goal of the modern systems today is to reduce that residence or contact time without losing a substantial amount of conversion.001 seconds. since the MSCC design is about 0. W. but the dry gas is also reduced by more than 20% as a result of the reduced time. Of course. and the desired product slate. Modern FCC units equipped with closed cyclones for rapid catalyst/oil disengaging and state-ofthe-art feed injection system for rapid feed atomization and vaporization allow the use of higher activity catalyst. In order to obtain the reduction in residence time to about 0.500 bbl/d after our revamp. higher riser outlet temperature. A severity increase is required to gain back conversion. higher catalyst-to-oil ratio. the type of catalyst being used. Low dry gas and good gasoline selectivity have been demonstrated in two commercial installations. One such system. PETER G.temperature increase from 980°F to about 1000°F when the residence time-is reduced from 1. and shorter riser residence time in order to maximize conversion while minimizing the over-cracking of gasoline to LPG and dry gas. we have conducted a number of FCC pilot plant experiments to look at very short contact time cracking. The improvement comes largely at the expense of LPG. In May 1995. The order of magnitude of time required for vaporization is 0. As you reduce the total system residence time in the reactor.6 seconds (conventional) to 0. cracking the feed to product. the preferred time is between 0. Although traditional riser systems have operated in the 2 to 3 second range. very little of the diesel boiling range material in the 70 Heavy Oil Processing . and as 1 see it. diffusion of these high molecular weight feed molecules into the active sites on the catalyst.. As I remember chemical thermodynamics. This type of performance will be required to realize the benefits of ultra short residence time. the conventional residence time in risers has been on the order of 1 to 3 seconds. what you give up is some conversion of that feedstock. The rapid end of riser separation techniques used today will be inadequate. and what their conversion objectives are. the refining industry will likely move this way as well. I continually hear extremely low numbers for preferred contact times. UOP and BAR-CO signed an agreement that gives UOP exclusive licensing rights for the MSCC technology. The gasoline yield increases by about 3 wt % to 4 wt % with the selectivity increased by several points.4 seconds based on outlet moles. MARK SCHNAITH (UOP): We need to keep in mind an important principle with regard to residence time. UOP licensed a 100 mbpd MSCC unit in the U.

the gasoline increases by about 5% absolute or more. were made at the same time. and what your process objectives are. They are faster and cheaper. If you had to make a choice between installing radial feed nozzles on the reactor riser or installing modern riser termination devices in the reactor. and the riser termination change to the vortex separator was probably 50% more costly than the feed nozzle revamp. we would do them both at the same time. as I am sure everyone else is. and a close coupled cyclone system was installed in 1994. we would select the high pressure radial feed nozzles on the reactor riser over a modern riser termination. KELLER: Yes. what you want to change to. but we are not sure if improved coke make was fully realized. which says the diesel fuel went through untracked. A “minimum residence time” modern riser termination system would cost several times more and would have to be part of a total unit upgrade to be able to handle the changes.feed was converted. SHEN: I agree with all the panelists’ comments that. There is no doubt in my mind that if you must take one or the other. Installation of the close coupled cyclone system resulted in reduced dry gas. and we chose to delay doing any work with riser termination devices until a later time. you must examine your situation. but typically have a project payback measured in months. It only made 3% slurry with a 1% carbon residue feed. and diolefin production. Typically. and the coke selectivity is improved. you are going to have to increase contact time or increase temperature. we spent $2. all other things being equal. all the heavy oil can be cracked in a very short contact time. Ask yourself what your configuration is today. Improvements when changing from one radial feed injection system to another are I am glad to hear the panel agrees with me. and radial nozzles can give you excellent results. The one thing I can say though. coke. allowing even further yield gains. we chose to change both feed nozzles and termination devices at the same time. but we thought. ROSS: Ideally we would like to install both upgrades to our unit. When differentiating between feed injection and riser termination the distinction between the two must be appreciated. The feed nozzles are a quicker. you take feed nozzles. But when you want to crack something in a 650°F to 750°F boiling range. In our particular case. It depends on what you are changing from. PETER G. The unit I am referring to ran at 1025°F reactor temperature. we are also very tight on capital. So it simply says. is that the riser termination in the reactors is going to be more expensive.5 million total for both of the changes. A new feed system would cost on the order of $l. Again.5 million and would provide better selectivity and an estimated 4% increase in conversion. we would be limited on catalyst circulation and minimum coke make. which would you choose? VAN IDERSTINE: roughly half of the above. Almost all of the bottoms was cracked in that short contact unit. When I asked this question to one of our process engineers who holds two riser termination device design patents. This unit made light cycle oil of 36 cetane number. and then evaluate both of them. feed rate and feed composition. we recently completed a study to determine what would give us the best return on our investment. to obtain the maximum benefit. he selected the feed nozzle over the riser termination device. But we just put in the 71 1995 NPRA Q&A Session on Refining and Petrochemical Technology . yes. If we had to choose one step first. ANDREWS (Consultant): Stone & Webster and other licensors have converted many axial feed injection systems to radial injection systems with dramatic results. Once one has optimized the feed injection system. we would choose the radial feed nozzles over riser termination devices. the focus should be riser termination as there is no point in preserving an inferior yield. In our case. If we installed the modern riser termination without other modifications. The improved feed nozzles were installed in 1989. We had the luxury of only installing nozzles when we were looking at both nozzles and riser termination. It almost totally goes through unconverted. Then apply your own economics. Installation of the new feed nozzles did result in improved yields. So how high do we have to go to convert diesel boiling range in a catalytic cracker? QUESTION 21. which would allow more catalyst circulation. Feed injection creates the yield pattern that riser termination seeks to maintain. the dry gas reduces by 20% relative. MORGAN: Valero chose to install both improved feed nozzles and close coupled cyclones in the unit. It would have been nice to change one and then the other. HANSEN: This is one of those “it depends” responses. The riser termination would increase conversion by minimizing coke. It is difficult to quantify the relative economics of these two items as other unit changes impacted unit yield patterns. lower cost upgrade to the unit. Our answer to that question was clearly the feed nozzles give you the greatest return on your investment.

decreasing gasoline end point.5 numbers. rather than a more efficient riser cyclone. So the payout for the closed cyclone system is more variable.): Any FCC mechanical upgrade should start by installing a set of “high-efficiency” feed nozzles as well as “uniform” delivery of a regenerated catalyst. the shape of the gasoline boiling point curve for each refiner. and the subsequent yields destroyed any further payout for installing the extensive. At a given conversion level. PHILLIP NICCUM (The M. TOLEN (Rocky Mountain Salvage & Equip. The two main advantages of radial versus axial feed injection are improved catalyst hydrodynamic (uniform catalyst density) and protection against reversal of feed into the regenerator. These changes were reported in the 1993 NPRA paper number AM-93-55.nozzles. and also reduces the gasoline volume by about 15 vol%. Right now we are moving that cut point around as the conventional gasoline limits dictate. The impact on RON is variable and will depend on the specific boiling point curve of the gasoline. i. REZA SADEGHBEIGI (RMS Engineering. For a unit where the product slate and the capacity allow operation at very high temperatures. If a refiner has a sloppy cut or the end point fluctuates. the heaviest 10% of the heavy FCC naphtha contains about 30% of the sulfur in the whole stream. Kellogg Company): Going from an axial feed injection system to a radial feed injection system will pay out in almost every case. keep old-style shower head nozzles or open pipe systems). DELBERT F. For a unit with a very large disengager. the payout is going to be higher. Regarding the other variables. the only way to quantify the octane change is to look at the actual distillation. without first modifying the feed nozzles (e. The most common option that refiners appear to be doing today is lowering the gasoline cut point. only stable reaction vapors passed into the RTL...g. assuming maximum gasoline product is desired. The payout for a closed cyclone system or a dusted cyclone system that eliminates vapor residence time in the disengager is a much more variable calculation. For example. In the 1994 transcripts feed hydrotreating and product hydrotreating were also discussed as options. Decreasing the catalyst-to-oil ratio will also decrease the gasoline sulfur and RON. In our particular stream. we see that lowering the cut point from a T90 of about 380°F to about 300°F reduces the gasoline sulfur by about 40%. lowering reactor temperature or changing catalyst-to-oil ratio. as the reactor vapors leaving the riser spent a long time in the reactor disengaging vessel where they cracked further. the payout is going to be higher. And also. there is not much control over the gasoline sulfur. It is good. the cheapest way to get out of this without spending a lot of capital is to change the cut point on the heavy FCC naphtha. you will coke the reactor transfer line.e. radial feed nozzles all the way. The speed of mixing the oil and catalyst is most important. EMANUEL: We feel. refiners should make sure that their column operation is well controlled so that there is good control in the gasoline end point. QUESTION 22. W. of course. This did not occur prior to SCT RTD installation. Neither of these. Also related to changing cut point. If there is room 72 Heavy Oil Processing . decreasing catalyst-to-oil ratio. is a very satisfactory way of reducing sulfur while maintaining gasoline octanes. If you change out a RTD for a short contact time (SCT) RTD. Since each refiner has a unique gasoline boiling point curve. expensive riser termination design(s). from some ofour pilot plant data. Inc. IAN JACKSON (BP Oil Company): I totally agree with everyone so far regarding installing good atomizing feed nozzles as a priority before changing the riser termination device (RTD). and increasing naphtha recycle. What FCC operational changes can be made to reduce the sulfur of the FCC gasoline with minimum impact on octane? Gasoline sulfur can be decreased by the following operational changes: decreasing reactor temperature. There are several things that come into play. Thus. if you are starting with an inertial separator device. SOLIS: The sulfur distribution in the products is largely controlled by sulfur in the feed. The refineries had to shut down within the year due to coke buildup in the reactor transfer line (RTL). the payout is going to be higher for a closed cyclone system.): DEADY: I agree that feed nozzles are far more important than termination devices. They were basically not vaporizing and cracking the feedstock in the riser. Two of our competitors’ refineries in Europe installed direct coupled cyclones (DCC) and kept their existing shower head feed nozzles. Another option that was reported in both the 1993 and 1994 NPRA transcripts is to recycle naphtha to the riser which can result in about a 20% reduction in gasoline sulfur with up to one number increase in RON. the gasoline sulfur can also fluctuate greatly and changing the cut point might not have as great an effect on reducing the gasoline sulfur. thus condensing the reaction vapors in the RTL as coke precursor liquid. we have laboratory data that show that decreasing reactor temperature by about 40°F decreases the sulfur in gasoline by about 7% and decreases octane about 1.

QUESTION 24. We do not use antimony. In some cases in the summertime. the other co-current. Conversely.2. Counter current typically has achieved mixed results. This route appears to have more sulfur-reducing potential for the front end of the gasoline. we have reduced the lift gas to the riser. however. Catalyst manufacturers have tested formulations that will reduce the sulfur in gasoline.25 to 0. We have also seen stripped sour water used successfully as a washwater. EMANUEL: We currently use lift gas in our UOP FCCU. During situations of increased yield of light gases to the point where we are wet gas compressor limited. The other one says 1 gpm/1000 bbl of feed is adequate. the most commonly used source is main fractionator overhead water. The flow of the washwater is extremely important. and keeping in mind that you are trying to both dilute cyanides and remove some of the solids from the system. In it. we can create a situation where there will be serious erosion/corrosion. there have been announced several processes for downstream of the FCC. As I said earlier. We typically run with a nickel plus vanadium in the neighborhood of 2000 ppm to 2500 ppm. to first stage after cooler. and the antimony is doing additional passivation. That also will cause an extremely serious corrosive environment. We suggest that people go with the co-current flow whereby the flow goes from main fractionator overhead. Where people have extremely high cyanide levels or a serious problem with hydrogen blistering. that actually would be a worse problem to deal with than if we did not have a water wash in the system. These obviously are predicated on the fact that there are certain operating conditions on a unit. processing high metals feedstocks. Having said that. If the calculation was done correctly. This work is still in its early days. does the use of a metals passivation agent provide additional benefits? DEADY: PAUL FEARNSIDE (Nalco/Exxon Energy Chemical Company): It has been our experience that the benefits of metals passivation technology on units with lift gas are 50% of the benefits you would receive on the units that do not have the lift gas.15 to 0. it is not appropriate to reduce the amount of washwater that is used on the overhead. Typically about 50% of the sulfur in gasoline boils between 380°F and 430°F This can be an octane rich portion of the gasoline.to reduce the gasoline boiling range. We are aware of two rules of thumb concerning how much washwater should be used on an FCCU. Finally. The implication is that the lift gas is doing some of the passivation. I have to tell you that we are not comfortable with either one of them. QUESTION 23. but I suspect that the effects are somewhat additive. we have removed lift gas completely to try to maintain FCC feed rates. whereas the end point distillation change reduces the back end sulfur. all the water flashes and whatever solids are carried back with the water are going to stay in the system where the water was injected and flashed. then the same amount of washwater is required. which will remove sulfur from the gasoline product with minimum reduction of octane. compared to the more typical FCC operations on the order of 0. Their hydrogen dropped when they switched from their previous catalyst to their current catalyst. a significant amount of sulfur can be moved into the LCO product. what is the preferred operating procedure when lower quality feed causes an increase in the yield of fight gases? In units with lift gas. our feeling is that even if the feed is hydrotreated. but the principle has been demonstrated in commercial trials. People have used two different schemes: one is counter current. What water rate is required for adequate washing of FCC overhead systems as well as gas plant systems? What quality of water is typically used? Can the rate be reduced when FCC feedstocks are hydrotreated? POTSCAVAGE: I am only going to address the second part of this question. We prefer to use a Simulation Sciences program and model the overhead and compressor after-coolers to determine how much water is actually required to do what it is supposed to do. If too much water is added. I looked at our ECAT database for the second quarter of 1995 to see which refiners who use lift gas were also using antimony in their operation. but not all units operate under the same conditions. On the last part of the question. indicating that the use of a metals passivation matrix also provides benefits over and above those obtained from lift gas. and eliminating it from the gasoline product can have an impact on octane. since normally main fractionator overhead water is recirculated in this situation. One says 2 gpm/l000 bbl of feed is adequate. Another refiner who uses lift gases is also usingacatalyst that contains a nickel passivating matrix. to second stage after cooler. They reported their experience in the 1994 transcript.3 antimony-tonickel. This has not been quantified. and I only found one refiner. if too little water is added in the overhead. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 73 . In fluid catalytic cracking units practicing riser lift gas technology. they have actually gone to the extent of using boiler feedwater. The next part of the question deals with washwater sources. they reported antimony-to-nickel ratios on the order of 0.

configuration. QUESTION 25. but sometimes intermittent. we just commissioned a high pressure hydrotreater ahead of the FCC.” April 1990. “Carbonate Stress Corrosion Cracking of Carbon Steel in Refinery FCC Main Fractionator Overheat Systems. Steam condensate is not only more expensive. but that did allow us to trim back considerably on the polysulfide use. In some bend.0 gpm of sour water per 1000 bbl/d of feed is typically recycled to the overhead line on a continuous. On the topic of the water quality. the combination of the high catalyst flux and high steam rate can result in a catalyst flow stoppage in the stripper. not catalyst circulation limitations. Cyanide production is a function of Total N in the feed. the makeup is often unclear — fresh or recycle sour water. stripping steam. An article published by NACE can be used as good reference: NACE Paper.pressure receiver where it is collected and directed to the sour water stripper.e. In a long.5 gpm to 1. over half of the total water “recycled” may be fresh. ROSS: Pertaining to the third part of the question. As noted.000 1b/sq ft/hr with some approaching l. and I want to emphasize that we agree co-current is better than counter current in the flow arrangement. Most UOP FCC units run to other limits before catalyst circulation limits are reached. PAUL FEARNSIDE (Nalco/Exxon Energy Chemical Company): We are finding it is not so much a question of how much washwater. The preferred injection means has been shown to be from low pressure to high pressure or co-current with the process flow to take advantage of the higher contaminant solubilities at higher pressures. but stripping performance will deteriorate as flux rates over design are used. Potscavage. standpipe angle. WEITH (Unocal Corporation): I agree with most of the comments Mr. vertical standpipe with a good catalyst hopper design. What are maximum attainable catalyst flux rates for standpipes and spent catalyst strippers? SOLIS: This issue was discussed at length in several recent Q&AS and by Mr. Because of this. Potscavage made. but how that washwater is contacted against the flowing gas stream. care must be taken to simulate the system to ensure that there will be liquid to wash the tubes and that not all of the water vaporizes upon injection. No. We use cold condensate which also has a corrosion inhibitor injected to lay down a corrosion barrier. If the FCC is a resid unit. Many units run up to 900. If you do not have the proper nozzle technology in place and do not have adequate scrubbing/contact between the water and the gas stream.. well aerated. i. usually air blower or wet gas compressor limitations bottleneck the unit. basis.). not coming from the reactor. 206. Normally a design range of about 100 1b/sec/sq ft to 200 1b/sec/sq fi is used with an upper limit of about 250 1b/sec/sq ft for revamps. I have one comment. or U-bend configurations. Standpipe velocity and flux rate limits are somewhat subjective. it may also be low in conductivity. you are just not going to do the proper job. For a gas oil cracker. etc. slanted. depending on the catalyst properties. Eventually. Approximately 0. thereby allowing for only intermittent or infrequent use of additional fresh water injection. The more interesting question is what are the turndown concerns? A flux range of about 50 1b/sec/sq ft to 100 1b/sec/sq ft. At the WGC interstage cooler. less than 100 ppb.SHEN: JAMES D.000 1b/sq ft/hr. When you inject polysulfide material into the water for cyanide control. We monitor with the spot test for cyanides using iodine and starch solutions. 1 gpm to 2 gpm of sour water is injected per 1000 bbl/d of feed and collected for injection into the high. we feel that the stripped sour water is a very good resource. The cold condensate is monitored for excessive oxygen content. and length. the total reaction system steam rate can approach the total 1 gpm to 2 gpm. Although a total washwater rate of about 1 gpm to 2 gpm/l000 bbl/d of feed is typically reported. nitrogen type.000. it is important that the water have a high conductivity level to ensure the polysulfides will suspend in the washwater. The reactor stripper will circulate everything the standpipe can handle since it is larger. a flux rate of 275 1b/sec/sq ft to 300 1b/sec/sq ft has been demonstrated. The ultimate standpipe circulation limit will depend on catalyst entry condition and physical properties. KELLER: As unit capacities are pushed to the limit. ROSS: We follow UOP’s recommendation of 2 gpm/ 1000 bbl of feedstock. making sure that it stays negative. The makeup of this recycle water depends on the amount of “fresh” water entering the overhead system as reactor steam (dispersion steam. regardless of the washwater flow rate. The usual remedy for an over-fluxed stripper is to increase the stripping steam rate to try to improve its performance. the higher flux and velocity are actually preferred to reduce the time for deaeration in the nonvertical section of the standpipe. We did not change our washwater rate. and reactor operating conditions. is a difficult transition zone where bubbles in the standpipe tend to stagnate — the catalyst velocity equals the bubble 74 Heavy Oil Processing .

In another case. The only problem is that very large line sizes must be used if one designs at this flux rate. A theoretical choke condition can be calculated at fluxes above about 1200 1b/min/sq ft depending on the baffle spacing. Experience has shown that often in these strippers the mass flux is in the neighborhood of 1200 lb of catalyst per foot squared per minute. and it is commercially being demonstrated in three FCC units. Effect of Mass Flux on Stripper Efficiency 1995 NPRA Q&A Session on Refining and Petrochemical Technology 75 . As for catalyst strippers. the commercial unit saw a 40°F decrease in regenerator temperature and enjoyed the result of increased catalyst circulation rate and conversion. if you will. Kellogg Company): I would like to discuss some experiences related to annular strippers. on the left. The curves on the graph below show. the flow becomes extremely stable again as the flow is now dense or pack flow. W. Mobil has developed a proprietary baffle design that has been demonstrated to extend the efficient range of an annular stripper. Below this flux. and it also falls at a high mass flux rate and is falling because of the entrainment of the gas down the stripper. The flux rate indirectly reflects stripper residence time and vapor-catalyst relative velocity. a poor stripping efficiency. At a certain point the efficiency falls. typical flux rates of 600 1b/min/sq ft to 1200 1b/min/sq ft have demonstrated good performance. A flux as high as 1500 1b/min/sq ft has been encountered. which typically have a riser running up through the center of the stripper. and there is excessive entrainment of hydrocarbons to the regenerator or. This new baffle design is being offered by Kellogg. the stripper efficiency versus the mass flux rate.rise velocity resulting in stagnant bubbles. This is a difficult region and is observed during each start-up where the best method is to push through this zone as quickly as possible. but the performance was fairly poor as measured by high hydrogen in coke values. The curve on the right is the density curve. PHILLIP NICCUM (The M. In one case where it was installed. detailed surveys around the stripper showed that the percentage of the coke that was entrained hydrocarbons dropped from 15% before the revamp to 5% after the revamp.

which include pressure balance and regenerator pressure control. However. In one refinery we are aware of.5 fps. All one has to do is take a piece of filter paper.5 fps. QUESTION 27. It is a much simpler test to run and easy for operators to do. System problems that have been encountered relate to interactions between the various pressure controllers on the combustion air blower. What problems have been experienced with flue gas expander operations when implementing FCC advanced controls? FRONDORF: Our FCC advanced control scheme has worked very well with no real problems to the unit operation or the expander. Texas refinery catalytic cracker without problems in the expander section.25 fps superficial velocity is claimed with no added catalyst losses. particularly temperature constraints. the regenerator velocity is about 4 fps with catalyst losses roughly twice that expected in a new unit designed for about 2. QUESTION 28. but it is not the controlling signal during normal operation. the bed becomes turbulent and the term “bubbling” does not technically apply. there is a ferrocyanide complex. our multivariable advanced controller does not directly control the expander. Its set point can be changed by a single output (software) controller to minimize the expander bypass control valve opening. What are maximum attainable superficial velocities in a bubbling bed regenerator as they relate to cyclone performance? ROSS: HANSEN: As the velocity in a bubbling bed increases beyond about 2 fps to 2. 4. This shows that the 76 Heavy Oil Processing . Our expander inlet and bypass control valves are controlled by the reactor/regenerator differential pressure (hard-wired) controller. but our feeling is that they are of academic value because the absolute cyanide value in the overhead is not necessarily indicative of whether there are going to be problems or not. The hard-wired controller is allowed to range from +5 psi to -5 psi reactor-regenerator differential pressure. We have installed and are operating our advanced control/optimization controls on our Corpus Chrisri. We are aware of an extensive distillation method that is described in “Standard Methods of Water and Waste Water Analysis. There have been no problems with the expander caused by implementation of these controls. regenerator. which indirectly determines the reactor. We prefer to use what is called a spot or Prussian blue test. Lower velocities will shift the CO combustion and heat to the regenerator bed and away from the cyclones and will reduce afterburn. the entrainment rate of catalyst to the cyclones clearly increases dramatically and almost exponentially with velocity such that losses will increase even though the cyclone efficiency will increase with higher loadings. First.5 fps to 3 fps are a good design range. However. For reference. it is a very tedious test. There are several points that should be considered. and put a couple drops of ferric chloride onto the filter paper. however the diplegs must be long enough to properly pressure balance and large enough in diameter to handle the flow. and expander. if you have constraints on downstream equipment from the expander. Our multivariable advanced FCC controller directly sets the suction pressure to the wet gas compressor. pour some overhead water on it. One should examine interactions specific to one’s unit when implementing advanced controls. or an existing cyanide by running the sample as is. Can any of the panelists suggest a method that works for measuring cyanide? What levels of cyanide have been found to cause problems? POTSCAVAGE: Part of the optimization program involves lowering regenerator pressure by partially bypassing flue gas around the expander. The regenerated catalyst slide valve differential pressure is also programmed to restrict the advanced controller during unusual conditions. the power recovery economics should be included in theoptimization software. (Losses due to fresh catalyst addition must be added to this figure. a general rule of thumb I use is 2 1b/hr loss per 1000 bbl/d for a typical high-efficiency.QUESTION 26. However. regenerator. Cyclones can be made to handle very high catalyst loadings.5 fps to maintain catalyst retention with losses near original design. two stage cyclone system in a moderate pressure regenerator operating at about 2. KELLER: Practical cyclone loadings of 2. and expander pressure. This requires less steam in the cyclone area and generally will provide smoother regenerator burn operations. If the filter paper turns blue.” It gives very good results. Second. The results obtained are very accurate. Most refiners tend to limit the operation of their regenerators to about 3. the advanced controller is restricted to +2 psi to 0 psi reactor-regenerator differential pressure. In another unit. they also need to be considered in the optimization software. It will give you total cyanide by proper treating of the sample.) JOHNS: Valero has implemented advanced controls on the heavy oil cracker.5 fps to 3 fps.

and a bluish tint indicates ferrocyanides and trouble. no other vessels showed any damage. Inc. Typical specifications range as follows: Gravity. viscosity @ 210°F of 80. WEITH (Unocal Corporation): Mr. BS&W 1%. a Canadian company has come up with a design called Beta Foil that looks much better to me. however some operators have noted a simple color check of the washwater where a yellowish tint indicates adequate polysulfide additive to control corrosion. KELLER: Almost all West Coast FCC slurry oil goes into the carbon black market or 0. Power stations can accept higher levels with a typical sulfur specification of 2%. if you can get into the market.05%. sodium 10 ppm. aluminum 200 ppm. It just seems to be much more practical. It has several salient features that I like. Then a top assembly that consists of the pressure gauge and a thermometer that snaps on through an O-ring.2 to 1. cst @ 122°F Sulfur. They consist of a pad that is welded on the vessel. QUESTION 29. BMCI 126. potassium 2 ppm. pour 60°F. vanadium 300 ppm. As I said.1 1995 NPRA Q&A Session on Refining and Petrochemical Technology 77 . KELLER: for a pressure increase. It has a vacuum-type attachment. Keller mentioned something about hydrogen probes. However. and typical specifications are: viscosity 250 centistoke.70 carbon steel plate used in our original primary absorber exceeded the specification for inclusions caused by impurities. you can generate more data and have a much better understanding of what is going on in the unit. We have seen hydrogen activity jump above 3 psi per day from our probes when the free cyanides jump above 10 wppm. and what are typical specifications? ABRAHAMS: EPA method 335 is a reliable method used by Ultramar and most regulatory agencies.1 wt%. We charge only hydrotreated feed (less than 3000 ppm Total N) to our FCC unit. and SFH 0. It covers several square feet. the specifications can be different. Our free cyanides vary from 1 wppm to 4 wppm in the washwater effluent at 2 gpm per MB/D of FCC feed. The sample should be collected to ensure no air is allowed into the sample bottle. A limitation of 200 ppm alumina typically sets the maximum catalyst content at about 1000 ppm. pour 60°F. California in 1992. sulfur 3%.cyanide is reacting with the metal in the overhead and is a clear indication that a better corrosion-control program is needed.5%. We have yet to see any pressure buildup in them. Typical specifications are: API of 0.): How the water sample is collected is also important in obtaining accurate cyanide results. Other outlets include asphalt or coker feed. flash 150°F. A small amount is sold into the domestic industrial market.5% sulfur Fuel Oil market which is exported to China or Korea. pentane insolubles 20%. The consensus in the earlier panelists’ discussions was that whatever you have. Filtration may be required to meet solids content specifications. it could probably pass that O-ring as well. Carbon black and needle coke are attractive markets if the stringent product specifications of density. BS&W 0. So. We put hydrogen probes on our FCCU in Wilmington. ash 0. and you monitor for a vacuum being broken rather than looking Slurry oil is typically blended into the fuel oil pool or disposed of in a coker. and asphaltenes 6%. wt % less than 1 to 8 80 to 180 0. The ASTM grade 516 . I am not satisfied with the way they are put together. One market is heavy cutter for fuel oil. REZA SADEGHBEIGI (RMS Engineering. Occasionally the quality of the feed and HCO or bottoms oil are in the narrow range required for carbon black or needle coke applications and the bottoms oil is then a high-value component. ROSS: The ASTM methods for measuring cyanides in waste water are D2036 and D4282. ash 0. Since then.15. For carbon black a 500 ppm ash limit and 2% S limit are imposed. What markets exist for FCC slurry oil. flash 140°F. Another market is carbon black feedstock. I think that if the hydrogen were tenacious enough to get through a steel shell. this is a very quick and easy test for the operators. The feedstock must be very aromatic and the cracker operation carefully controlled with a bottoms cracking catalyst to produce this material. Absolute control of the cyanide level is difficult without frequent analyses. sulfur 6. JAMES D. viscosity. Although the actual levels of cyanide that cause problems are unclear.0 wt%. °AP1 Visc. many control to about 20 ppm to 30 ppm in the washwater. and boiling range can be met. We replaced our primary absorber from hydrogen blistering after 7 years of operation without always providing 2 gpm of washwater per MB/D of FCC feed. ROSS: We have been in two markets for FCC slurry oil. Increasingly tighter specifications are placed on fuel oils and now alumina content must be controlled to avoid engine fouling.

Other yields should follow correlations for heavy gas oils since the deasphalted oil is a product of physical separation and not a cracked material.4 905. conversion.1 74 48.9 0. The higher paraffin content in the DAO (versus VGO) explains these results. When this value is relatively low (MCRT=1. The °API of our slurry is typically around zero.7 wt%). however. % Gasoline Yield. % Total Gas Yield. For example. When processing solvent deasphalted oil in an FCCU.5 92. We have observed that the catalytic cracking selectivities may correlate with the DAO carbon content. the DAOs we have encountered have conversion precursors or gasoline precursors 30% to 50% lower than VGO of the same source. in the flue gas and products. % Coke Yield.7 4. We heard several rules of thumb this morning on the effect of FCC properties on conversion.80 59.JAMES D.93 66 44. and we have to keep reminding them to keep their coke drum temperature up. We counsel about this.5 15.5 DAO-2 112.6 4. to make sure not to set up a refractory recycle if coker gas oils are charged to the FCCU. a four Conradson carbon deasphalted oil will make coke more like a two Conradson carbon heavy gas oil. A change of ~ 330 ppm equivalent Ni (Ni + 0. the lower the slurry °API the better it is for the coker. VGO Aniline point. The FCC operation therefore will also be variable between clean gas oil and contaminant-laden resid performance with all of the usual warnings about metals contaminants. and LPG yields are higher than that for a typical VGO. These catalyst systems provide a much higher stability in overall activity than a conventional 78 Heavy Oil Processing .4 921. I must admit when I first saw the question. The next important parameter is nitrogen. Approximately 500 ppm nitrogen affects conversion by -3. however. Given that there is very little in the literature on the subject and specific results of our work are not yet ready for publication.4 63 43. wt % Viscosity. and this has been in NPRA QSLA transcripts before. The feed-derived coke due co contaminants as measured by Conradson carbon tests may well be less than equivalent asphaltene rich resids. gasoline. The following data are provided as an example of the previous statements. due to the immediate effect on conversion and yield selectivities. % LPG Yield. WEITH (Unocal Corporation): SOLIS: We feed our slurry to our coker to prevent it from making shot coke. I can only offer the following remarks.0 13. the quality of DAO is really on a sliding scale between VGO and VR. the conversion. The poly-aromatics are generally higher. to FCC feed hydrotreating units. % 3 DAO-1 114. especially basic nitrogen. measured by the n-d-M method. The second parameter is aromatic carbon CA content. The final parameter is contaminant metals. I have co caution. Kg/m @ 15°C MCRT.25V) affects conversion by ~ 1 vol% and regenerator temperature by ~ 20°F. if the DAO has a large carbon content (MCRT=2.75 vol% and regenerator temperature by ~ 10°F. °C Density. Reports from our ROSE licensees indicate that as an incremental FCC feed.0 18. QUESTION 30.5 The most important parameter is Conradson carbon residue (CCR). Kellogg Technology Company): As with the previous question on deasphalted oil (DAO) quality monitoring. due to environmental constraints.5 21. especially Ni and V.8 4. However.0 15. DAVID SLOAN (The M.8 912. but the coker supervisors keep forgetting. This quest-ion is supplementary to Question 11 from the General Processing Session.70 46.5 1. An ~ 1 wt% change in CA affects conversion by ~ 2 vol% and regenerator temperature by -20°F. depending on the depth of deasphalting. Conradson carbon in the deasphalted oil may behave in the FCC as a gas oil with Conradson carbon residue of the square root of the DAO Conradson carbon. including deasphalted oil (DAO). Our rule of thumb for the effect of CCR on FCC yields is that a 1 wt% increase in CCR will decrease conversion by approximately 2 LV% and will increase regenerator temperature approximately 50°F. We have designed catalyst systems chat are in FCC feed hydrotreating units which process as much as 40% deasphalted oil.5 17. As I understand it. I hoped that by the time of this meeting we would have some pilot plant data co share on the characterization of deasphalted oil as FCC feed. RICHARD STREET (Criterion Catalyst Company): We see a trend in refiners charging heavier fractions. A refiner might also want to look at sulfur levels. In general. resulting in more catalytic coke for a given conversion level. however.24 8. cst @ 100°C MAT Activity. ROSS: H. and gas yields are lower for the same coke production.3 2. gasoline. how do incremental yields and performance correlate to solvent deasphalted oil properties? DEADY: It is quite clear that the solvent deasphalted oil (DAO) properties affect the FCC yields. precise commercial measurements are difficult as the amount of DAO in the feed blend is typically less than 20%. and the contaminant coke is also a factor. W.8 wt%).

or. sometimes they do not even realize that they are running it in the FCCU until they see a decrease in conversion and an increase in trace metal contaminants on their ECAT. if there is a choice.).3 +1. When processing lube oils. as a general rule. which can act to redisperse and activate nickel that is already on Tests and operating data show that the used lube oils convert very well at the FCCU. we typically see an increase in calcium and/or zinc that tracks identically with the loss in conversion. These levels are directly associated with lube oils. The metals. Generally. When we look at our ECAT database. etc.7 -4.2 In general terms this is consistent with a lower feedstock quality similar to DAO where one might expect about half of the yield potential of virgin gas oil. we have actually observed a number of refiners in the past year that have operated this way. But I found that most refiners do not have a choice. the surface area that is measured by nitrogen method was unaffected. the additive solvent package can contain halogenated hydrocarbons.6 of a microactivity number for every 100 ppm of calcium oxide increase. One refiner saw a 4 number drop in the microactivity and also noticed a loss of the water pore volume that we report on their ECAT sheet. potassium. What are the incremental yields and performance changes expected from the FCCU when processing visbreaker gas oil? ROSS: One refiner reports the following yield shift when replacing 15% of a VGO feed with visbreaker gas oil: Gas+ LPG Gasoline (190°C) LCO DO Coke 1. When we measured the pore volume with mercury. The high paraffinic molecules crack easily. copper. And for zinc we see a range anywhere from 0. indicating significant amounts of lube oil being processed. SHEN: To answer the first part of this question on industry experience when processing used lube oil in the FCC. used lube oils tend to contain plenty of alkali metals (calcium. magnesium.9 of a microactivity number to about 2 microactivity numbers for every 100 ppm of zinc oxide. the data did not show a noticeable impact on gasoline octane and olefin yield. All those tend to deactivate the cracking catalyst. causing additional coke and gas. you would rather process the paraffinic ones.0 wt % -2. It appears that one mechanism by which used lube oil deactivates catalysts is by pore plugging and shutting off the active sites. QUESTI0N 31. Obviously. The net effect has been achieving the refiners’ FCC feed specifications and several of the performance targets at economically attractive FCC feed hydrotreating cycle lives. I have data from a couple of MAT studies comparing VG0 feed and visbreaker feed by themselves. Finally. we saw that the larger pores in the 700 to 2000 A range were reduced and were actually shifted down to the 100 to 700 A range. In addition.e. (All of the usual conditional statements regarding crude type and processing severity apply.4 +4. and tend to make more coke and gas than conventional FCC VGO feeds. Additional contaminants (for example. We thought that was interesting and took a closer look. because the amount of lube oil fed into the FCCU was relatively small. and that is probably their first clue that something is going on.FCC feed hydrotreating catalyst system processing deasphalted oil. zinc. However. In general. and vanadium) will produce higher coke and gas. zinc.. lube oil stocks contain fairly high amounts of FCC catalyst contaminants. indicating plugging of the larger pores. A typical approach people use is to process this stream through a rerun fractionation tower (or vacuum tower). if you have spare capacity in 1995 NPRA Q&A Session on Refining and Petrochemical Technology 79 . Examples of this are sodium. which looks in more detail at the larger pores. QUESTION 32. will have the tendency to stick with higher boiling range molecules. and vanadium. The highest zinc numbers that we have seen are about 3300 ppm. The loss of conversion ranges from about 0. manganese. i. In fact. The distillate from the rerun tower can either feed to the FCC directly. However. and these metals can rapidly deactivate FCC catalyst if any significant volume is processed. lube stocks can be either very paraffinic or very aromatic. FCC operators generally see a dramatic decrease in their ECAT activity and unit conversion. the visbreaker gas oils are fairly aromatic and refractory.6 +0. and then another study that compares the VGO feed with 5% and 10% blends of the visbreaker feed.) DEADY: In general. magnesium. Finally. we observed something this year that was interesting.2 of a microactivity number to 0. The highest calcium numbers that we have seen are about 6000 ppm. What is the industry experience when processing used tube oil in the FCCU? What pretreatment is recommended for this stream? DEADY: the ECAT. a lot like coker gas oil.

% Gasoline. % HCO. TOLEN (Rocky Mountain Salvage & Equipment): If you would like to come out. What levels of particulate removal from FCC flue gas can be achieved by the various technologies? ROSS: to recommend such a system when regulatory limits are less than 75 mg/Nm3 . But. wet scrubbing. cyclones in the regenerator will not meet this specification by themselves. and electrostatic capture. ninety miles west of me is the smallest commercial FCCU in the world. which range from multiple moderately sized cyclones housed in a separate vessel to many very small horizontal cans or vertical swirl tubes in a separate vessel. Cyclonic separation systems. As a word of caution. However. Stone &Webster would be reluctant 80 Heavy Oil Processing . The varying influence of fresh catalyst additions and normal catalyst attrition make reliance on this type of system for very low discharge levels risky. Due to the requirement to provide efficient contact between a fine mist of water and flue gas.the FCC feed hydrotreater. you can send it there to remove these metals. % Coke 62 43 14 26 17 5 350°C to 550°C Used Oil Cut 81 58 20 15 7 3 DELBERT F. Other systems. Sulfur transfer agents in the regenerator offer a simple means of controlling this “additive” particulate matter and can make the difference between say 120 mg/Nm3 and 100 mg/Nm3. can achieve particulate emissions reduction to about 75 mg to 150 mg/Nm3 on a consistent basis. which for some refiners. When very strict regulations are in force. % Total Gas. and it runs on nothing but used lube oils. an electrostatic precipitator is the clear choice. such as sintered metal or ceramic filters. The metals content in this cut were as follows: Fe V Ni Cu Na 137 <10 not <20 ppm ppb detected ppb Cr Zn Al Pb not detected 300 ppb 38 ppb not detected 20 ppb When we compared the catalytic cracking of this cut to that of a typical VGO. The newer third stage cyclones with many small cyclones fitted inside a vessel claim efficiencies approaching 50 mg/Nm3 in the discharge. The SO3 in the flue gas stack is a prime example. a wet scrubber system similar to the Belco or Exxon scrubber can be used. we have made a trial with a distillate cut (350°C to 550°C) from a used oil collecting factory. has been the difference between compliance and non-compliance in the past. Effluent levels as low as 10 mg/Nm3 have been achieved — at a price — with typical levels well below 50 mg/Nm3. when the environmental limits are below about 200 mg/Nm3. we observed the following differences: VGO Conversion. Environmental Control QUESTION 33. catalyst capture automatically results. 500 bbl/d. The design of these cyclones should not be pushed in an attempt to meet the limits. The types of commercially proven particulate removal technology available fall into three categories — cyclonic. SOLIS: We have never directly processed used lube oil in our units. Another consideration when looking at particulate control is the level and control of condensibles which are typically included in particulate tests. The fractionation bottoms can be sent to the coker. rather the appropriate downstream units should be designed to handle normal regenerator emissions. When present or future flue gas treatment for SOx and/or NOx is required. are still in the proving stages but potentially offer extremely low effluent levels. Do not jeopardize the regenerator cyclone design by pushing the design limits in a futile attempt to meet emission limits. % LCO. Effluent concentrations of 50 mg/Nm3 or less are common. upon request from the Madrid Environmental Authorities.

40 are precipitated. EURIPOS series. up-to-date. KELLER: Our FCCU was built in 1982 with an electrostatic precipitator. Nowadays. under the premises of identical operational constraints applied. and 7 are in the slurry oil. dry/cyclonic rype third stage collectors. of course. and highly advanced mathematical modeling processes. i.ABRAHAMS: At one of our plants. Cyclonic third stage separators have come a long way. These are similar to filtering modules but have a rigid pipe electrode axially mounted inside each module. unproven. Although his statement may have been made in a purely self-serving manner. Over the years their design. last but not least. would be capable of rendering almost twice the collection efficiency as compared to that of a so-called multiclone cyclonic device (employing a series of small diameter tubes). The enlarged particles and mist droplets are removed from the flue gas by mechanical impaction created by the filtering spray nozzles. The scrubber easily makes the permit maximum allowable particulate level of 0. the refiner. allowing an actual check of the mathematical models. but instead relies upon modern. MANFRED OEHNE (Polutrol — Europe): I would like to submit a statement in favor of the modern. to arrive at emission levels of 70 mg/Nm3 to 80 mg/Nm3 (dry) is absolutely no problem. Electra filtering modules can be used if significantly lower emission levels are required. A positive electrical charge is also induced on the filtering spray which allows the particles and mist droplets to be subjected to two removal mechanisms. allowing even better designs via fine tuning of the rather complex processes taking place inside a cyclone. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 81 . But even to check emission levels for purely environmental reasons. He furthermore claimed that based upon an identical particle input analysis. the mathematical modeling will be steadily improved. The device was successful in removing mass from the stack up to about a ton and a half per day.8 to 1. overall functionality. For example. of course. HANSEN: Valero installed a Belco EDV Scrubber on the HOC unit flue gas in October 1994. Three go out the stack.57 lb of particulates per 1000 lb coke burned.2 micron can be achieved without a hitch. so-called large diameter cyclones (he defined 40-inch diameter to be the preferred size) are capable of achieving drastically higher collection efficiencies in the vicinity of 75% to 80%. the engineering companies and. Where do we go from here-what does the future hold in store? With great certainty. and unscientific. we had one of those million dollar “Oh-shoot” projects. is a requirement that should be pursued with diligence by everybody involved. We lose 50 tons of catalyst a month. I take objection to a statement offered by a speaker from the floor who suggested that third stage collectors that have a number of small diameter cyclone tubes inside a common vessel will protect expander turbines by grinding up particles. is wrong. the apparent nonlinear behavior of particle densities in a force field needs to be explored further.e. Our recent stack tests have measured 24 mg to 34 mg of total particulate matter per dry standard cubic meter. it nevertheless leaves the impression that a few large diameter cyclones. but their overall efficiency normally would be in the 40% to 50% range. The EDV scrubber filtering modules employ condensation of water vapor onto submicron particles to increase their mass. is not an outdated seat-of-the-pants design approach. This undoubtedly will require a closer cooperation between the catalyst manufacturer. Such performance is very much in the range of scrubbers and ESPs. but it had little impact on opacity because it was ineffective in moving particulates below 10 microns. The trial was made because of some success that had been reported in reducing opacity in the power industry with this kind of device. mechanical impaction and electrostatic attraction. There seems to be just no alternative to a modern third stage collector whenever a power recovery installation operates downstream of the FCC generator. His statement. and catalyst collection capabilities have been improved dramatically.. A series of recent tests performed at two European refineries involving our modern dry type third stage collector. The basis of such impressive performance. Power usage by the electrodes is very low since the current levels are on the order of 10 milliamps. Testing of operating systems in the field. We installed a multi-cyclone separator downstream of our CO boiler in an attempt to influence our opacity without having to go to the higher metallurgies required upstream of the CO boiler where it is hotter. Modern third stage separators (dry type) have proven they are capable of rendering emission levels in the vicinity of 50 mg/Nm3 (dry) and below. On a final note. And this impressive performance can be achieved without any underflow system and/or fourth stage collector required. the designer of dry type cyclonic third stage collectors. referring to a previous question (Question 21). Electra filtering modules have been used extensively on incineration and SO3 applications. The scrubber was instrumental in allowing Valero to be the first petroleum refiner to win the Texas Governor’s Award for Environmental Excellence in 1995. has produced clear evidence that fractional particle efficiencies on the order of dsm(5e) = 0. The ionizing effect of the electrode gives the wetted particles and mist droplets a negative electrical charge. this collector type is a wise choice.

so we do not use them on a regular basis. as well as rotate the plug ports for flow direction changes. and comparing that over time. There is one other method that our Corpus Christi refinery utilizes. In 1993 a WFMT examination of the coke drum ODs identified a crack in a girth weld of one of the drums. we use them periodically on a planned basis. At this efficiency. KELLER: We have purchased. We used Custom Industrial Automation of Canada to inspect our four coke drums.Contrary to what was claimed. We will follow up with UT and visual testing of the suspected points. We have been very satisfied with all three techniques. KELLER: We are aware that Wilson-Snyder has developed a system to fully automate their switch valve. B. QUESTION 35. We will automate this electro-hydraulic unit with an on-board Programmable Logic Controller (PLC) which will be tied into our Distributed Control System (DCS). either during the year or before a scheduled turnaround. We have had a high rate of success locating cracks before they become leaks. 82 Heavy Oil Processing . particularly in the areas of recurring cracking and bulging. and this type application has also been fully automated. emission standards of 6 mg per normal cubic meter can be met without additional separation equipment. Has anyone automated a Wilson-Snyder type switch valve for totally remote operation? It so. ROBERT L. It is named U Plus and uses an ultrasonic imaging technique for crack detection. ABRAHAMS: We can confirm the approximate price. We do not have direct experience with one. The new actuator uses hydraulic pistons to hammer seat and unseat the plug of this highly mechanical valve. We found no bulges. FRONDORF: CITGO has used acoustic emission (AE) testing for locating cracks in coke drums. but I am not very familiar with it. This type of hydraulic actuation replaces the upper jackscrew collar of the valve. To ensure proper drum isolation during coke cutting. These four clad-lined coke drums have been in service 14 and 25 years. so there is not a lot of disruption to normal operations. acoustic emission In January 1995 CIA was contracted to conduct a laser evaluation and videotaping of our four 24-ft ID coke drums. to date. This has aided in predicting when cracks and bulges are beginning to develop.g. What results were obtained and what were the approximate costs? FRONDORF: Pall blowback filtration systems remove more than 99. I want it to be known that it is really the other way around. laser inspections). how was the lowering and raising of the collar accomplished? JOHNS: We have not had any experience with the Wilson-Snyder type valve. The PLC will control the time-sequenced piston operation either locally or from our remote DCS. particularly older drums.000 and indicated no bulging. The mapping is performed utilizing the existing drill stem rigging. an electro-hydraulic actuator from Wilson-Snyder.9% of the solids in the flue gas. but not installed. We also use these data for finite element analysis when designing new drums. These tests are performed during the normal coking cycle and do not disrupt operations other than the building of scaffolding for the placement of the AE sensors. The use of ball valves in this service is becoming more common. which is normally used to raise and lower the plug assembly. (e. Residual Oil Upgrading-Delayed Coking Mechanical QUESTION 34. The laser evaluation cost $80.. BROWN (Pall Process Filtration Company): testing. but we are going to use those data to provide a baseline for future reference and to support our plan to extend the shutdown interval on that unit by 12 months. We have utilized automated laser bulge mapping to size and track the growth of bulges in the coke drums. We have also utilized high temperature strain gages to monitor coke drum stresses during the coke cycles. rather. The costs are fairly high. It may replace acoustic emissions in the future and they say it is considerably less expensive. Normally it can fit into your cycle on a reasonable drum cycle time. It is done immediately after coke drum cutting is complete. an operator will still manually close an isolation valve between the Wilson-Snyder switching valve and the full drum. The new actuator should reduce operator exposure to the existing WilsonSnyder coke switching valve. The laser evaluation conducted in 1995 did not identify bulging associated with this crack. We are preparing to buy two such valves for one of our Lake Charles cokers. Please discuss new technologies to monitor coke drum bulging and cracking. This technique has proven to be a very useful tool in evaluating the condition of drums.

JOHNS: We have not heard of anything catastrophic. Both facilities have nine-chrome. we now have a short cycle on this particular heater for the first time. We have not noticed anything due to biological causes. One needs to consider that heater design may have a lot to do with the ease and even the feasibility of pigging most heaters. specifically in the following areas: a) impact on tube life from metal loss. so we have not done any decoking of that heater in the last three years. we used mechanical pigging once. The key to solving this problem is to have a good water settling tank operation and to keep the water velocity in the cutting water system below 6 fps or 7 fps. QUESTION 37. JOHNS: We do not do any mechanical pigging of our coker unit heater.): At one of our plants. Describe your experience with mechanically decoking (“pigging”) coker heaters. QUESTION 38. For some reason.): I would like to poll the panel and the floor. Due to the relatively high cost of pigging. which show. Is anyone using the “new” 9Cr V tubes in their furnace? How have they performed? JOHNS: We have not used the “new” 9Cr V tubes. we have seen increased corrosion rates from pitting type corrosion in the coker cutter water We have practiced pigging a number of times on the cokers in two of our refineries. Steam/air decoking on our coker heater is a procedure we have done for many years and can complete with a 24to 36-hour feed outage. To date. We believe that erosion is caused by coke particles. but really did not find very much coke. This is how we detected plugging and high pressure drop in this line. Furthermore. we have not experienced any significant metal loss due to the pigging. MORGAN: Neither of our facilities has 9Cr V tubes. Does anyone experience extremely high corrosion rates in coker cutting water systems? We have identified our cause to be microbiological and have suspicions that our problem is aggravated by coking sludge. The intensity of color gives you the degree of temperature. I think it would be possible to shock the system if it is truly a biological problem. we have been reevaluating the steam/air 1995 NPRA Q&A Session on Refining and Petrochemical Technology 83 . With regards to the exact question on pigging. b) downtime required as compared to steam/air decoking. What solutions have been successful? SHEN: We use slides of a thermographic scan of the large lines coming out of the coker drum. c) impact on heater run length. Perhaps something went wrong in the procedure. and I am not aware of any failures of that nature. d) success at removing coke formed as a result of high sodium in the feed as compared to steam/air decoking. or are you aware of. What we have seen is that most problems are erosion rather than corrosion. We believe we do not have justification for the metallurgy yet. We are usually quite successful. a coke ball near the top. so I will keep it short. one plant has successfully mechanically pigged the lines. GARY HUGHES (Conoco Inc. Inc. We had observed that usually all laydown material had been cleaned by this pigging until this last time in July. We do a steam/air decoke. since there are usually other mechanical items at the coker which preclude the use of this material allowing a longer cycle length for the heater tubes. MORGAN: We have two cokers. We have not seen a cutting water system corrosion problem caused by microbiological factors. We optimized our coker unit operation such that the cycle time between steam/air decokes has increased from about 40 days to over 200 days. Chemical treatment is a very expensive option. a catastrophic failure in terms of a rupture of a coke drum? Or has the failure mode been constrained to cracking and bulging? ABRAHAMS: system. The stream-to-stream downtime required for pigging a furnace is typically 2 to 2½ days. from a thermal color gradient. VAN IDERSTINE: My answer to this question could be off the mark. after pigging. We have not found a cost-effective way to treat it. QUESTION 36. FRONDORF: All the failures that I am familiar with have been in the cracking mode. On the vacuum unit heater. we are consistently producing anode grade green coke.KEITH OSBORN (Farmland Industries. Have you ever experienced.

We feel that the stress on the drums is minimized more by 84 We would not recommend draining the drum by opening the bottom head. During the coke drum cooling/cutting part of the coking cycle. As for the question of coke quality and drum integrity. which we have done as we have shortened cycle times over the years. and the coke in the drum is not always in a homogeneous form. Louisiana refinery still has a big steam step. QUESTION 40.decoking technique. If the operator is having difficulty draining the drum because of blockage. Any water injection would convert to steam. At the Corpus Christi plant. but there is always the potential of over-pressuring the drum. Rarely do more than half the bottom head bolts need to be removed to establish an adequate drain. immediately after switching to blowdown.. FRONDORF: Our cokers are designed to drain the quench water through a line teed into the bottom head gooseneck. have changes in coke quality or drum integrity been observed? SHEN: We split our naphtha in the coker. It is more on the order of 5 to 10 minutes. We have not seen a coke quality change when we have eliminated this step. maintaining a total cool-down time. but it is considerably shorter than the half hour to one hour mentioned in the question. Concerning heater run lengths between decoking. This has been done when we were either short of HCU feed or long on reformer charge. and an inhibitor/disbursement material will be required for this light coker. It requires that a two-man team wearing proximity suits remove a continuous quarter to half section of the bottom head bolts. After the big steam step. Occasionally we get a plugged drum or drain line. We believe it could be a hazardous operation. The obvious negative aspect of feeding coker naphtha to any hydrotreater is silicon poisoning from silicon in the antifoam. the big steam step has been eliminated. We take a 350°F end point on our light naphtha and we send that over to our heavy naphtha unifiner. we have found that the pigging technique does a much better job of removing nonorganic deposits. Do you regularly drain your coke drums by opening the bottom head flange? What safety issues need to be considered? How is the quench water collected and returned to the quench water storage? KELLER: The answer to this question is yes. of course. i. We have seen several refiners skip the big steam step to shorten cycle time. cold water can hit the hot metal wall. To drain the drum in this case. And since doing so. we see similar run lengths between furnace decoking when utilizing the pigging technique versus steam/air decoking. feedback indicates that refiners cannot tell any difference. which sometimes build up in the return bins of the furnace tubes. the coke bed and the drum are still at very high temperatures. Therefore. we are concerned more about drum integrity than coke quality. allowing us to reduce the stream-to-stream time from 4 days to 3 days. People adjust the water rate by watching how fast the pressure rises. the water does not distribute as well as the steam. or for any other reason. The resulting localized thermal stresses could potentially cause vessel cracking. we believe the utilization of pigging versus the steam/air decoking method must be evaluated on a caseby-case situation. Concerning Item D of the question. Has anyone eliminated the “big steam” step in order to reduce cycle time? If so. at certain economic times. What are refiners doing with their coker naphtha besides sending it to reformers and FCC units? VAN IDERSTINE: Process QUESTION 39. As for coke quality. The only situation that we know of when refiners do this is when the draining system is completely blocked and there are no other options. we have been able to improve our steam/air decoking procedure. we follow a written procedure. we begin the quench cycle immediately after switching to blowdown. The other concern we have is that when you add water to a hot coke drum. You need to watch the heat transfer on the preheat exchangers. The heavier coker naphtha goes to our distillate hydrotreater. They start with the bottom head bolts furthest away from the catwalk and work their way back to the platform. water is injected into the bottom of the drum.e. There is a possibility that channels in the coke bed exist. SHEN: The Lake Charles. charged some of the light coker naphtha material to our hydrocracker and that has usually been in the range of a 360°F to 370°F end point. After the small steam cycle. The water goes directly into the sluiceway and is recovered in the dewatering/clarifier system. QUESTION 41. we would Heavy Oil Processing . steam is injected into the bottom of the full drum (called “big steam") for one-half to one hour. JOHNS: We have. If a channel is directed toward the vessel wall.

Try to run your delayed cokers in a manner that will avoid the potential of plugging your bottom drain. but we do on our fluid coker.recommend putting in additional drain lines located in the straight side of the coke drum shell approximately 1 ft to 2 ft above the conical section. FRONDORF: Our LYONDELL-CITGO joint venture had been processing used lube oil as vapor quench to the coke drum overhead vapor line. If the drain line restriction problem (blockage) happens frequently. barricades. We do not regularly drain the drum by dropping the bottom head. FRONDORF: At one of our plants. Most of the benefit has been in public relations from working with the local authorities. 8% naphtha. We have had essentially no pretreatment. Where that would become necessary. First. Last. VAN IDERSTINE: QUESTION 43. which would automatically swing out. We have not had any corrosion problems or any other operating problems as a result of this. the downstream hydrotreater that processes the coker naphtha experienced corrosion from the outlet of the reactors through the cold flash drum circuit. Is anyone pressure draining coker drums using nitrogen. The cause of this corrosion was apparently organic chlorides contained in the used lube oil fractionated into the coker naphtha stream. At our Corpus Christi. evacuate the area below the drum prior to lowering the head. If you ever open the bottom head flange without proper draining. One potential problem with pressure draining is that too high a pressure difference across the coke bed could collapse your coke bed. and 3% coke. Chloride levels as high as 40 ppm were noted in the naphtha. We have since discontinued processing the used lube oil. or simply making the drain line larger. would break down to a yield of 4% butane. ensure that the drum has been adequately cooled. steam would be a lower cost selection over nitrogen. We are currently on 13-hour cycles and are considering going to 12-hour cycles. but not least. how to control the spilling of the hot water and loose coke on the deck. One line failure was experienced. what has been the impact on drain time? SHEN: We do not have experience on a delayed coker. we have a written procedure that follows the same guidelines that were previously mentioned. ABRAHAMS: I agree with the others. We have been collecting used lube oil from local company service stations and also from Delaware. We do not know of any refinery pressure draining the coke drum using nitrogen or steam. We made sure that the oil did not contain any free water after transfer to an existing fuel oil tank. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 85 . it may be because of shot coke production. if any. No pretreatment was performed on this oil. in addition to providing recycled benefits. resulting in a blockage problem in the lower section of the coke drum. and if so. What has been the experience processing used lube oil in coker units? What pretreatment is done. The only time you get into that situation is if your bottom drain becomes plugged for some reason. Most drums are equipped with some type of hydraulic or pneumatic lift for raising and lowering the bottom head. At least you can recover the water. Texas refinery. Several safety issues that could come up if one decided to go to a drain-by-a-bottom-head method would be: the conversion of the bottom flange to a remotely operated studless flange along with the spool piece on the feed line. No corrosion problems were noted in the coker itself. 82% gas oil. three steps are recommended. ensure that the bottom head can be held in place while the flange bolts are removed. Second. 3% pentane. However. we have an automatic remote-operated unheading device that gives us more flexibility when this problem occurs. and what were the benefits? Has corrosion been experienced in the fractionator overhead lines? JOHNS: I agree with the previous comment. It is something you would normally try to avoid. just upstream of the preheat furnace. QUESTION 42. etc. Personnel involved in this step should wear protective equipment when unbolting the head. No corrosion problems have been associated with this procedure. We estimated the benefits to be that the oil. we have had a very positive experience for 2 to 3 years collecting used motor oil and injecting it at a slow rate into the coker. If something must be used.

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