1995 NPRA Q&A - Heavy Oil Processing

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
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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 peoples 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. Exxons 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 units 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 950F to l000F, 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.
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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 " 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 300F to 500F 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 slurrys 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.
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Two methods have been mentioned in the past, perhaps not quite so new, that seem to be the most frequently used to clean the systems. The first is periodic flushes with a hot light cycle oil (LCO) to dislodge the sludge, with polymer chunks collecting in a good filtering system. I have heard from one refiner that occasional use of a heavy naphtha has been used, with a caution that you break free almost all the deposits in the circuit and you have a good filtering system. 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. 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. With this arrangement, they are able to operate without a spare and run continuously for three plus years. There are also in-line scraping systems, which have, been marketed through ELF and Total, to continually break free deposits. In every instance, the use ofgood filters at the exchanger inlets is mandatory. Finally, if you look back over the last several years at all the techniques to monitor operation andcomposition, the one that sounds the most promising is monitoring of the C7 insolubles (asphaltenes). This procedure has a strong analogy to what is done to monitor primary fractionator fouling in ethylene plants. As I understand from the literature, people tend to control to between 2% and 5% and have fairly good results without fouling. VAN IDERSTINE: Our fouling of slurry exchangers has dramatically decreased in the past 2 to 3 years. We have increased our focus on maintaining adequate exchanger tube velocities. Our rule of thumb is a little bit lower than the velocities mentioned earlier. We control between 4 fps and 7 fps. We also control the slurry gravity to about -5 API. We do have the LCO hot flush connections that Mr. Ross mentioned. 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. As a cost reduction method, we stopped adding antifoulant into the system and did not see an increase in our fouling frequency.
DEADY:
turnaround. Another refinery was shutting down every 2 days to clean the slurry exchangers. Since they instituted an antifoulant program, the shutdowns have been more on the order of 9 to 12 months.
EMANUEL:
I do not have a horror story quite that bad. We periodically back flush the slurry exchangers on-line, but that tends to have a fairly small effect. So we revised our piping so that we can pull exchangers one at a time and hydroblast while the unit is on-line. That tends to be on a yearly cycle. We still have not been able to justify the antifoulants in slurry service.
HANSEN:
We have successfully used an antifoulant program in the slurry loop for several years. The program was originally started to reduce and control fouling in the packed sections of the main fractionator. The program uses high temperature dispersant and inhibitor chemistry, which was selected by the chemical vendor based on testing of our slurry. There have been instances when excessive catalyst carryover has caused fouling of the slurry loop steam generators, which have required mechanical cleaning. The fouling deposits were loose and mainly catalyst, and were easily removed by hydroblasting.
JOHNS:
Fouling will usually occur two ways: from coking and from asphaltene precipitation. If you stay in a certain range, usually antifoulants will work. A rule of thumb on the asphaltene precipitation is that if you are using a charge from highly paraffinic crudes, 3% of the naphchenic-type crude into that will usually be the limit. Above that you will get precipitation of asphaltenes in hot slurry exchangers and preheat heaters. On the other side, with the napthenic crude, you can go up to 15% paraffinic material. If you get out of those ranges, generally, an antifoulant will not work.
JAMES W. JONES (Turner, Mason & Company):
Generally we think that slurry antifoulants will do a good job of preventing the pumparound system from fouling. However, they are not necessarily very effective in cleaning an already fouled system. I have a couple ofstories from refiners who have been successful in using antifoulants. One was operating a slurry system that had to be shut down about every 11 months to clean the fouled exchangers. When they switched to a good slurry antifoulane program, the pumparound system operated continuously for about 27 months. It probably would have operated longer, 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. We found this to be as effective, and sometimes more effective, than the use of antifoulants. Antifoulant programs that provide on-site technical service do improve operator control over unit operating parameters. This type of program significantly reduced slurry exchanger fouling in one refinery with which we are familiar.
Depending on the configuration of the FCC bottoms pumparound, an effective on-line cleaning could be a continuous injection of 3% to 5% of either HCO or LCO
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into the inlet of the bottoms exchangers. You may also want to have a spare bundle on hand to minimize downtime.
Catalysts
QUESTION 6. 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, so we do test our ECAT when we receive it. If we suspect a problem, or if there is a discrepancy with a vendor, we conduct testing at our research center. They can test all the properties, and typically before we run any new catalysts in the unit they conduct a full range of fresh and de-activated catalyst property tests. This provides a reference point for specifications and vendor tests on the new catalyst because there are such discrepancies between the different vendor tests.
ROSS:
We have developed a very extensive process of selection before any changing of catalyst. This process is designed to choose the optimum catalyst for our feedstock and unit operating conditions. Once we have selected 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. The quality control program to carry out with the samples has been previously agreed upon with the catalyst producer. If the sample does not meet specifications, we can reject the truck or ask for liquidation damages. The test always includes MAT Activity (>72%); Na2O (<0.45%); and Attrition Index (DI<8). Be sure to cross-correlate, as well as possible, the analytical methods of the refiner and the catalyst supplier. If you do not, you will have serious problems comparing results. One of the major concerns of this program is sampling. We have developed a procedure in which we take one sample from the truck for the supplier, one as reference and one for testing. We have developed this program over six years, and we have only observed problems on two occasions. One was low attrition and the other was a case where they sent the truck to the wrong refinery. Generally speaking, we are very satisfied with the quality of our supplier.
PARKER:
Generally, we monitor the fresh catalyst using the data sheets from the vendor. We receive most of the tests listed on the data sheets for each shipment with the exception of attrition, MAT, and surface areas. Those are only done occasionally, maybe every third or fourth truck. We do compare these numbers to the specifications we have for our catalyst. If there is a problem, we call the vendor and usually we are compensated on the next shipment or by making a price adjustment. We have really not had many problems. One problem that we have had occasionally is that we may be getting material that is within specifications, but continuously on the low side of the range on a particular property. We call and usually get an adjustment toward the target value. Once in a while we will put equilibrium catalyst (ECAT) in our resid cracker. We have had instances where we had
Some refiners rely on the quality assurance programs and certifications of the catalyst vendors, whereas others are more proactive. Typically, fresh catalyst is sampled randomly or each batch received is sampled with samples retained but tested randomly by the refiners central laboratory or research and development facility. Properties such as pore volume, surface area, chemical composition (zeolite, alumina, rare earth, and promoter/platinum content), attrition index, and particle size analysis are performed on perhaps 20% to 30% of the samples. One refiner cautions that particle size distribution can be tricky as sampling a large truck is not trivial due to settling/segregation during transit. Sophisticated high-volume users may request vendor process control charts and trend manufacturing control points and variables. Average values of variables can be monitored, as well as deviations from the manufacturers set points, to track consistency and control of the process to identify irregular batches. As for ECAT analyses, samples are taken either weekly or twice a week for analysis by the vendor. Response times of about one week are reported. When unit performance changes unexpectedly, samples are sent to the research and development or central laboratory for independent analysis of MAT, metals level, chemical composition, etc., and perhaps operation in a pilot unit using the feedstock from the unit in question. Results of these tests are then discussed with the catalyst vendor, possibly resulting in compensation. Good sampling and sample retention procedures are essential.
ABRAHAMS:
Our practices are similar co those of Mr. Parker. We rely heavily on our suppliers analysis and crosscheck periodically. We also have been very successful in dealing with the vendors directly for recourse on the rare occasions we have had problems. There was one instance a few years back, though, in which a supplier was unable to deliver suitable quantity and quality of a new catalyst. While it was painful, we parted ways for a couple of years and went with another supplier.
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DEADY:
A handful of our customers continue to monitor fresh catalyst properties. Several others have in the past, but most of that has been discontinued due to refinery and research and development cutbacks. The refiners who still do their own analyses analyze every shipment. The properties they monitor include chemical and physical properties, especially particle size and attrition and catalytic testing to measure activity and coke selectivity. Some refiners without internal laboratory facilities have sent random samples for third-party testing. One important caveat before starting this kind of testing would be to establish a correlation with your suppliers laboratory analysis. This would eliminate potential laboratory biases due to analytical differences and allow you to establish a baseline should discrepancies arise in the future. The refiner also needs to make sure they obtain a representative sample for testing.
HANSEN:
We also generally rely on the quality control sheets provided by the catalyst suppliers. In our case, the items of major interest are the fresh activity, rare earth, particle size distribution and hardness. We have found the need on occasion to send samples to third parties to confirm shipment quality and, like most, we would change suppliers if we felt we had a problem.
WILLIAM D. HENNING (Conoco Inc.):
We monitor fresh catalyst quality in a central technical support group and laboratories. We collect both vendor lot samples and truck samples of the fresh catalyst at the refinery. Typically, each truck sample is tested for composition by x-ray and for surface area. For some units, we also conduct attrition and particle size distributions tests. We have found in the past that some incidents of FCC performance loss have correlated to catalyst quality. We have worked closely with our catalyst vendors and have put in place quality control agreements for various composition and physical properties. There are specified ranges for each shipment and a narrower range for a six truck moving average. There are economic penalties associated with falling outside of some of these ranges. 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, but also the capabilities and driving economics of the FCC catalyst manufacturing process.
STEVEN K. PAVEL (Coastal Catalyst Technology, Inc.):
of potential contributors, testing and analysis are essential. In any case, units with high addition rates relative to the size of the circulating catalyst inventory ate most sensitive to fresh catalyst property changes. Fresh catalyst shipments are routinely sampled and tested. Delivered fresh catalyst properties are compared to specifications, shipment inspection reports, and previous deliveries. Minimum testing includes XRF and XRD for complete elemental analysis and crystallinity on each delivery. Profiles on new catalysts might include: XRF; XRD; surface areas, pore volumes and pore size distributions by nitrogen and mercury; pore volume by water; bulk and skeletal density; particle size distribution and attrition; TCLP; and full MAT yield tests unsteamed and after steaming for 4 hours and 16 hours. If a fresh delivery shows a significant change in XRF or XRD results, more testing is performed. Analyses of feedstock elements usually do not include all the deactivating contaminant elements in the feedstock, which are deposited on the fresh catalyst either routinely or as a spiked anomaly. Fresh catalysts are a source of the spent catalyst elemental constituents; without analysis of the fresh material it is difficult to calculate the deposition of contaminant elements. Fresh catalyst elements are analyzed by XRF, and, in certain cases, by ICI? X-ray diffraction is used to measure unit cell size and crystallinity, and to provide a qualitative analysis of mineral composition or phase. In several instances, the X-ray diffraction analyst was the first to identify changes in the fresh catalyst composition. It is generally accepted that any system under observation changes. The occurrence ofquality control situations can only be determined by sampling and testing.
Most refiners have operated for a long time without testing fresh catalyst. Terry, it would be of interest to know how many refiners are now testing catalyst all the time.
HIGGINS:
Could we have a show of hands of who tests fresh catalysts all the time? The audience show indicates five or six.
QUESTION 7. What success have refiners had at reducing FCC naphtha olefins wifhout losing octane (e.g., reactor riser temperature, 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, or a catalyst that does not meet specifications. Most often problems are detected in the 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, and they were also summarized in the Oil and Gas Journal, April 24, 1995.
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To reduce FCC naphtha olefins, refiners should use moderate reactor temperature, maximize catalyst-to-oil ratio, increase catalyst rare earth level to increased zeolite unit cell size, minimize catalyst matrix surface area, and use ZSM-5 to crack naphtha olefins. In order to reduce FCC naphtha olefins without losing octane, a combination of these approaches is probably necessary. If a refiner is currently using a low or no rare earth USY catalyst, we would recommend switching to a high REUSY catalyst plus ZSM-5. The switch to REUSY will reduce gasoline olefins by about 25% on a relative basis with an octane penalty of about two numbers, depending on the base octane level. The ZSM-5 addition will easily recover the loss in octane with no increase in gasoline olefin content. In fact, some studies actually show a decrease in gasoline olefins with the addition of ZSM-5. We know of other refiners who are already using REUSY catalyst. In these cases, they are planning to drop reactor temperature, then add ZSM-5 to regain the lost octane and LPG olefins. A drop of about 30F 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.
EMANUEL:
handle extra feed, any loss in FCC naphtha octane due to increased severity could be overcome by recycling LCO to the hydrotreater.
G. ANDREW SMITH (INTERCAT Inc.):
While we agree with everything the panel said, some refiners would like to maintain gasoline volume and increase octane without increasing olefinicity, and high silica-to-alumina ratio pentasils offer this possibility. There is also, as Mr. Hansen has indicated, a reluctance to drop the reactor temperature more than 10F. However, we have customers who have reduced the reactor by greater than 10F. They are adding a bottoms upgrading additive, BCA-105, to maintain or reduce bottom yields while maintaining or increasing gasoline yield with the lower reactor temperatures.
QUESTION 8. 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, especially the coke yield? Are there any other operational impacts (e.g., 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, so we had to apply for a Work In Progress adjustment in our refinery baseline. Olefins have been a problem for us. Currently we control olefins by maximizing catalyst-to-oil ratio in our FCC unit. We have tried moving reactor temperature moderately, i.e., 10F one way or the other, but have not seen much change in olefins. We have scheduled a trial of ZSM-5 early next year to see if that will help us. I would like to comment that the EPA approved method for testing olefins in gasoline works fairly well for blended gasoline. But we have found that the test for streams such as light catalytic naphthas, which have a higher percentage of olefins, is very erratic. I would like to have some comments from the floor if anyone else has had that same problem.
ERNEST L. LEUENBERGER (ARCO Products Company):
We recently completed a test run at our Los Angeles refinery where we analyzed olefin content using the EPA method, an NIR technique, and a GC technique. The EPA-approved method had the poorest reproducibility. We hope to use the NIR technique for process control. In addition to the methods that Ms. Deady mentioned to control olefins, I would add that if you have an FCC feed hydrotreater, you can reduce olefins by increasing hydrotreat severity. 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. This additive technology converts gasoline sulfur species to H2S. In the commercial trials, we observed up to a 25% reduction in full range gasoline sulfur. This reduction was corrected for changes in feed sulfur and gasoline end point. We saw no other changes in any of the other yields or the gasoline octanes. Further commercial testing is scheduled while work continues on improving the performance of GSR. Regarding conventional FCC catalysts, we have seen that changing from a low hydrogen transfer catalyst to a high hydrogen transfer catalyst will reduce gasoline sulfur by about 6%, based on our circulating riser pilot plant testing. Matrix surface area also impacts gasoline sulfur. In MAT testing, we have seen a correlation in gasoline sulfur reduction with the steamed matrix surface area ofcatalysts. The range of matrix surface area tested was from about 20 to 125 meters squared per gram. The higher matrix surface area catalysts gave a 15% to 25% sulfur reduction, compared to the low matrix surface area catalysts. From past experience, the percent reduction we have observed in microactivity testing has been somewhat higher than what we have observed in riser testing. We normally attribute this to the difference in contact time between the MAT and the riser. In commercial units, we do not always observe a significant reduction in gasoline sulfur when the matrix surface area is increased. The yield shifts associated with increasing matrix surface area depend on the specific type of matrix surface area,
51
but can include better bottoms cracking with the penalty of increased coke and dry gas, particularly with very high matrix surface area catalyst. If the FCC unit is constrained by the air blower or gas compressor, increasing catalyst matrix surface area may not be a practical option to reduce gasoline sulfur. That is the major reason we concentrated on the additive approach to reducing gasoline sulfur. The refiner avoids having to deal with significant selectivity changes in the base catalyst.
JOHNS:
I would cite some pilot unit testing at our Port Arthur research facility. We have seen on a variety of catalysts up to 10% reduction in FCC naphtha sulfur. Usually, high rare earth and high matrix activity catalysts tend to reduce the sulfur the most. The sulfur is observed to go to H2S and LPG products rather than to flue gas. We have also commercially tested a proprietary sulfur reducing additive in one of our units.
ROSS:
in gasoline, and this reduction will very much affect the FCC naphtha as a component of the gasoline. By changing the actual commercial catalysts, e.g., changes in rare earth (RE) content and/or different matrices, very little, if any, reduction of sulfur occurs. When using specific additives for sulfur removal, reductions up to 35% are achieved. However, the extent of that reduction strongly depends on the feedstock (crude source, EBP, sulfur content, etc.). Generally speaking, we have observed a linear relationship between the FQP (feed quality parameter, which depends on feed density, VABP, S, and aniline point) and the feed sulfur content, and the naphtha sulfur reduction achieved.
Naphtha S Reduction (%) 5 15 25 Feed FQP 76.8 79.2 81.5 S% 1.9 1.3 0.7
Circulating pilot plant work by one refiner has confirmed the 20% target reduction in full range gasoline sulfur when using these additives. But there seems to be the following trade-off with constant catalyst-to-oil ratio and riser temperature, i.e., a 3% absolute reduction in conversion, 1.5% absolute reduction in light catalytic naphtha with the heavy naphtha unchanged, and a 10% relative increase in the coke yield. Also, there is a reduction in the gasoline olefins, resulting in an octane loss of 0.6 RON and 0.4 MON. Obviously, the technology is new and developing, and these are only pilot plant results reported by one refiner. An important consideration is the conversion level at which the sulfur level reduction is attempted. At low conversion with some aliphatic species containing sulfur in the gasoline, 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. When attempting to attack the aromatics, coke production will likely increase. Although the fine-tuning of sulfur levels may be possible via this route, at present it would appear that feed treatment would be more effective. As an interesting aside, in our short residence time cracking pilot plant work, similar sulfur reductions were observed. A reduction in secondary reactions, possibly those creating stable aromatic sulfur species, has been theorized. However, there is also some dilution effect as the gasoline selectivity is increased at very short residence time.
SOLIS:
Thus, in some cases, sulfur reduction is clearly below 15%. On the other hand, the present catalysts (additives) seem to simultaneously increase the coke and H2 yields. As a matter of fact, coke yield increases 0.5 wt% for a naphtha sulfur reduction of 15 wt% to 20 wt%. Finally, although most of the sulfur is retained by the additive and hydrolyzed to H2S in the stripper, some still goes to the regenerator, increasing the SOx emissions.
In recent trials of INTERCATs bottoms upgrading additive, we have achieved reductions of gasoline sulfurs ranging from 20% to 30% with a significant portion coming out of the heavy gasoline cut. Refiners directly attribute these reductions to the use of the additive and not to cut point changes. However, at this time, the results of the sulfur balances have not been released; most of the sulfur removed is assumed to be in the form of H2S. The other benefits include improved bottoms upgrading and reduction of slurry viscosity. There were no changes in coke and C2 minus gas yield.
QUESTION 9. 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. Also, 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. You can either use it in cement or use it in asphalt as road base. For cement use, the cement manufacturers really do not care much about the particle size distribution since cement is fairly fine, even finer than FCC fines.
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We currently have discussed this application with cement manufacturers both in the U.S. and in Europe. In Europe, there are some metals limits on the equilibrium catalyst (ECAT). This would presumably be the same for the fines. The metals levels are 4000 ppm nickel, 8000 ppm vanadium, and 1500 ppm antimony. In the U.S. the major limit appears to be vanadium at about 8000 ppm to 10,000 ppm. Cement manufacturers worry about the vanadium content because it could attack the brick in the calcines and cause deterioration. As for using the fines in road base, we have experience with this application in Europe and over in the Asia-Pacific area. In Europe they have restrictions on the particle size distribution. What probably will cause a problem is that the fraction below 10 microns must be minimized, so I am not sure how practical this use would be for FCC fines in Europe. There are metal limits in Europe as well: 4000 ppm nickel, 7000 ppm vanadium, and 1500 ppm antimony. In the Asia-Pacific area, we are not aware of any restrictions on the particle size, so fines are probably appropriate for this use. Again, there is a limit of about 7000 ppm nickel on the ECAT or the fines.
FRONDORF:
Process
QUESTION 10. 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. ROSS:
Current disposition of FCC fines from both our refineries is to landfill facilities. Periodically we explore disposition to cement kilns when economical and available. FCC fines are classified on a characteristic basis per normal EPA guidelines such as metals, organics, etc., and, fortunately, not on a definition basis such as sewer sludges or waste water sludges. The characteristic classification has been nonhazardous industrial waste for typical fine properties of today.
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, August 28, 1995. The usual operational changes made to reduce catalyst losses and stack opacity include: reducing air rate (not a good choice), or replacing oxygen enrichment for some of the air; increasing regenerator pressure; changing to a more attrition-resistant catalyst with a higher particle density; reducing fresh catalyst addition and fines content of the fresh catalyst; reducing regenerator bed level, if cyclone flooding is the problem; monitoring and regularly unloading third stage cyclone catch vessels to avoid flooding; and considering SO3 reduction methods as condensibles in the flue gas impact on the opacity. Very often, an overlooked attrition source is the actual cause of high opacity problems. High-velocity jets generate fines which increase the overall loss and disproportionately increase the opacity reading. All possible attrition sources under direct operator control, such as jets from instrument and equipment purges, must be checked and rechecked. Other preventive actions include: continuous catalyst addition to avoid bursts of high losses; regular inspection and maintenance of the opacity meter itself, ensuring that the purged media is hot and dry and the mirrors are clean; and continuous sonic-type soot blowers, instead of daily mechanical soot blowers, to avoid bursts of losses.
VAN IDERSTINE:
We currently dispose of the fines caught in the underflow system with the equilibrium catalyst, which is sold to a local landfill. We have also disposed of this as a nonhazardous waste and have used it in cement manufacture. We also collect fines through our wet flue gas scrubber system. These are collected separately and sent out of the plant as a nonhazardous waste.
KELLER:
Our dry FCC fines are transported by pneumatic truck to a local cement manufacturer and blown into a dry hopper for later mixing. Wet FCC fines are transported to a different local cement manufacturer and bottomdumped into a liquid holding tank equipped with a mechanical mixer. Wet fines are segregated from dry fines, otherwise they would form a cake, which would be unusable at either facility. There are no other restrictions at this time.
I agree with most of those comments. 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. On the topic of attrition, monitoring your 0 to 40 micron size in your equilibrium catalyst is important. If the quantity in that size range is either stable or increasing during periods of high catalyst loss, then you probably do have an attrition source in your system somewhere.
PARKER:
On the catalyst issue, where there is an electrostatic precipitator operation downstream, you can alter the catalyst and sometimes that will change the electrical resistivity, which will impact how well the precipitator will pick up. Also, regarding flue gas concentration, sometimes the corona current on the precipitator will be impacted by the
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flue gas properties. We have observed that increased CO will actually help the corona current, and sometimes, on some of our precipitators, lowering the excess oxygen will also help. On the precipitators we operate, we do not necessarily see the same magnitude of change with the same adjustments.
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. The hoppers were almost full of catalyst with only small openings to the dump valves.
SOLIS:
I basically agree with what has been said. You might want to verify the regenerator catalyst inventory levels. If the level is too high, you have a reduced free board and you might be overloading the cyclones. If it is too low, you might have uncovered the cyclone diplegs. You probably want to check velocities of the primary and secondary cyclones to make sure they are in the proper ranges. Also, poor aeration and catalyst circulation could be causing pressure imbalances where you could have surging or fluctuating opacity problems. Poor wet gas compressor control could also create pressure imbalances which would have the same effect. I want to add to Mr. Parkers remarks on catalyst resistivity. There is actually a narrow range in which you can vary catalyst resistivity. Most catalysts used today have higher resistivity than the actual ideal level for precipitators, which is why most refiners also use NH3 in the ESP (to lower the resistivity to the optimum level). So even though it is directionally a good idea to change catalyst resistivity, it is not always practical to do so.
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. Catalyst quality, makeup amount, air distributor, and catalyst velocity in the process are key factors to control fines production. Therefore, considering only operating aspects, opacity is clearly a function of FCC catalyst physical properties. Several models exist that allow the quantification of attrition index, particle size distribution, and catalyst density effects on the opacity measurement. As a matter of fact, for the U.S. ranges of commercial fresh catalyst properties, R.G. 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 0.79 to 0.86 0.91 to 0.95 0.4 to 1.1
Clearly, attrition index has the largest impact on opaciry. The particle sizes that contribute most of the measurement ofopacity are products ofcatalyst attrition; the lower the attrition resistance of a catalyst, the higher the propensity to produce fine particles that increase opacity.
Flue gas opacity can be from catalyst fines or SO3 in the flue gas. We have found that maintaining control of the regenerator level and underflow system is needed to prevent fines carryover, which causes erosion, deposits on the flue gas expander, and potential stack gas opacity. Operation at low excess oxygen levels will minimize SO3 formation. We have the ability to inject sodium bicarbonate solid into the flue gas ahead of the wet gas scrubber for SO3 control, if needed.
KELLER:
We are particularly sensitive to the overuse of CO promoter. If you use too much promoter, apparently that affects the resistivity of the flue gas, which affects the efficiency of the precipitator.
DELBERT F. TOLEN (Rocky Mountain Salvage & Equipment):
We have tried a number of ways to improve the performance of our electrostatic precipitators. 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. This was somewhat effective but not dramatically so. We have tried to reduce the visible SO3 particulate by adding SOx reducing additive again with limited results. We have reduced the flue gas velocity by minimizing the excess O2. This seems to help somewhat, but may be related to pockets of catalyst that get swept into the flue gas at higher velocities.
We deal in equilibrium catalysts, and we see a lot of catalyst analyses. 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. I could not figure that out, so I called the refinery and asked if they recycled fines. They said they did not; rather they had a third stage separator, but they made little catalyst off it or the electrostatic precipitator. They hauled it out about once every 3 weeks, a couple hundred pounds. This unit retains an average particle size of 50 to 55 micron. They lose almost no catalyst. They have no problem with stack opacity at all. I called Mr. Ed Tenney of GE Environmental Services and asked what design was used for these cyclones to give that kind of retention. I have not received an answer yet. The following chart provides particle size data from this unit over the last 8 years.
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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 .28 .27 .28 .28 .28 .25 .27 .26 .27 .25 .26 .26 .25 .26 .26 .28 .27 .27 .26 .28 .27 .27 .27 .27 .28 .27 .27 .28 .27 .26 .28 .26 .28 .25 .28 .27 .28 .29 .27 .27 .29 .27 .91 .90 .91 .99 .93 .93 .91 .91 .91 .92 .92 .91 .91 .92 .92 .91 .91 .90 .91 .92 .91 .91 .91 .92 .91 .92 .92 .90 .93 .90 .91 .91 .92 .92 .86 .89 .86 .87 .86 .86 .87 .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 .28 .28 .27 .27 .27 .27 .27 .29 .31 .28 .29 .29 .29 .30 .29 .29 .29 .30 .30 .29 .29 .31 .30 .29 .30 .30 .30 .31 .31 .31 .30 .30 .30 .30 .29 .87 .88 .92 .90 .90 .90 .95 .88 .88 .88 .88 .87 .89 .87 .87 .88 .87 .87 .87 .88 .88 .88 .89 .89 .88 .89 .88 .86 .86 .88 .88 .89 .89 .90 .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. TENNEY (GE Environmental Services):
Yes, for several years now Mr. Tolen has been accusing us of designing special cyclones for one refiner and not offering them to any other refiner. 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
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specifications that we have used for about 80% of the currently operating units. We do not have an explanation for why this refiner has been able to retain the fines that they do. Their operating conditions are not unique. However, recently they have increased throughput, and their fines level and average particle size have increased. Therefore, it appears they have not been pushing the unit. If they continue to increase throughput, we expect their catalyst analyses will be similar to those generally found in the industry.
QUESTION 11. What upgrades are available to improve performance of existing third stage flue gas separators? SOLIS:
cyclones (10 I.D. or less). There are 50 or more of these cyclones in the separator vessel. One will find that these separators protect expander turbines because they grind up the enter particles to less than 10 microns, but the overall efficiency of this type of separator is only 40% to 50%. The other type of separator consists of 6 to 20 larger diameter cyclones (40 I.D.), usually in a vessel. Because of the small number ofcyclones and because these cyclones can have diplegs with valves, both of which tend to minimize circulation of gases from one cyclone cone to another, this type of separator has a collection efficiency in the range of 75% to 80%. The particle size analysis of the catalyst escaping from each type of separator is about the same, but the losses from the second type of separator are significantly less.
MANFRED DEHNE (Polutrol - Europe):
We have implemented an overall revamping of our FCCU at the Gibraltar refinery. We have installed a catalyst cooler and have increased by 20% the air flow to the regenerator. As a consequence we have also revamped and upgraded the third stage separator (TSS). Our TSS is Shell type and employs the conventional reverse-flow cyclone principle. The particulate level downstream TSS must not exceed 100 100mg/Nm3. Our original TSS had swirl vane tubes that were closed on the bottom and had two slots for the collected fines to drain. Any plugging of these slots will cause the separator to not function properly. We have completely opened those bottoms to allow easier catalyst fine drainage. We have increased the number of swirl vane tubes by 22%. We properly fitted the swirl assembly to keep it centered in the can to avoid cracks in the ceramic lining as it expands. The seal weld between the swirl vane tube and top tube sheet was done very carefully to be airtight, because substantial catalyst bypassing can occur if it is not. These items should be checked and maintained as required during turnaround to maintain proper performance.
I think we all should keep reminding ourselves that a third stage cyclone is a true and typical mass transfer device. All cyclones are typical mass transfer devices. Their behavior (operational), hence, is governed by the very same physical laws as those ofsimilar mass transfer devices. The mathematical basis is the fundamental Euler equations. In a sense, the principal design operants of cyclones may be compared to those of tubular heat exchangers, i.e., their efficiencies are inversely proportional to their diameters. As the overall heat transfer coefficient of a small diameter tube will be higher as compared to that of a large pipe, the fractional collection efficiencies of small diameter cyclones will be considerably higher as compared to those of large diameter cyclones. Hence, Eff (small diameter cyclone) >> Eff (large diameter cyclone) In addition, it is very important to realize that design parameters utilized should be in tune with reality, i.e., they should closely correspond to and reflect operating conditions realized in the field later on. The old truism garbage in, garbage out holds value for the design of third stage separators as well. If the initial design parameters specified are wrong, the third stage separator, in all likelihood, may not work properly as expected. However, not everything may be lost at this stage, as minor operational instabilities usually can be corrected at a later time with relatively little effort. Conventional cyclone systems (large diameter types), in general, react very unfavorably to changing operating conditions (turndowns). Their vortex stability is a function of their relatively large body geometry and volumetric flow of the continuum. Conventional cyclone separation efficiencies, thus, can drop quite drastically as a result. A perfect example is the changing operating conditions of internal cyclones inside the reactor/regenerator vessels. (They most often are the source of catastrophic catalyst surges occurring). Consequently, a third stage cyclone having only a small number of large
Based on conversations with Mr. Rick Miller of M. W. Kellogg about two years ago, I was prompted to check the installation of our critical flow nozzle on the underflow of the third stage separator. The unit was shut down to plug some tubes in the flue gas steam generator, and I discovered the nozzle was indeed in backwards. It makes an amazing improvement in efficiency if it is installed correctly. The efficiency about doubled. This is compounded by the problem that it was installed intuitively, or what maintenance people thought was intuitively the right direction, because it is easier to put together the way it was rather than the correct way.
EDWIN D. TENNEY (GE Environmental Services):
Basically, there are two types of third stage cyclone separators. One type has a large number of small diameter
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diameter cyclone tubes is more susceptible to operational instabilities as compared to one having a multiplicity of small diameter tubes, so-called modules, inscalled. But even a third stage cyclone with an assembly of a relatively low number of large diameter cyclones, with a little bit of effort, can be made to operate quite stably. The diagram on page 58 shows a modern third stage cyclone requiring neither an UNDERFLOW System nor a FOURTH STAGE COLLECTOR. In addition, in order to promote stable operations over a wide range of operating conditions, VORTEX STABILIZER DEVICES are installed. For orientation, the THIRD STAGE COLLECTOR shown is subdivided into three distinct pressure chambers: A, D, and E. Dust-laden gases enter the system at the upper inlet nozzle and are immediately expanded inside the FLUE GAS DISTRIBUTION PLENUM (A). There, the gas velocity is lowered to a level where solids back mixing is greatly minimized. A small size-large size solids particle disengagement process is initiated and promoted. In addition, a gas-solids separation mechanism is triggered (via saltation). Still traveling at a very low velocity, the flue gases are turned downward toward the horizontally arranged modular collectors (C). Large size solids particles, debris (such as liner material, having been carried our of the regenerator vessel), and clusters ofsolids material (such as catalyst surges), continue on their downward path never entering the modular collectors - and are temporarily collected inside the DEBRIS COLLECTION PLENUM (B). Material collected there is discharged via the DEBRIS/ROUGH CUT DISCHARGE (G). Solids material - already having been pre-sized and being of sufficiently small size - will enter the modular collectors via their tangential inlet horns. Inside each modular collector cell, a centrifugal force ofapproximately a hundred gs is imparted upon each solids particle introduced into the system via the gas stream. The internal collector cells separate the solids particles from the gas stream and discharge them into the FINES COLLECTION PLENUM (D), where the dust is removed via the SOLIDS FINES DISCHARGE (F). Final removal of the solids may be carried out by a typical underflow system, or by gravitational force only, e.g., into a separate FINES STORAGE VESSEL arranged underneath the THIRD STAGE VESSEL. Each modular collector cell moves cleaned gases outward and toward the CLEAN GAS PLENUM (E), where gases are discharged via CLEAN GAS OUT (H) upward and back into the main stream. All modular collectors are installed in a quasi-horizontal, helical fashion inside a pressure vessel, uninhibited by thermal expansion. The modular collector cells are interconnected via a grid-like construction, thus allowing free, uninhibited radial and axial expansion of the internal system. This design minimizes the buildup of stresses. Each modular collector cell moves cleaned gases outward and toward the CLEAN GAS PLENUM (E), where gases
are discharged via CLEAN GAS OUT (H) upwardly and back into the main stream. As can be seen, each internal cyclone is fitted with an internal vortex stabilizer device (patented), which turns this modern third staged cyclone into a very stable operating device. Correct positioning of the vortex stabilizers, however, is very important. Their location is very important. The position, by and large, is determined by the natural vortex procession. I need to point out that the geometric axis of the cyclone structure and the axis of the vortex should not be confused. They are not identical. Via installation of vortex stabilizers, operations of the cyclone collectors will become stable and predictable. As a result, the internal vortex finger will not jump to the wall when operating conditions change. Hence, it will not erode the inner liners and will not cut off diplegs as can be experienced often with old style, standard type cyclones. As already mentioned, this particular third stage separator does away, without compromise, with UNDERFLOW and FOURTH STAGE COLLECTORS. It achieves collection efficiencies of around 80 mg/Nm3 . Units rendering collection efficiencies of 50mg/Nm3 are already in service. On a final note, it is possible to revamp/upgrade existing/older third stage cyclones to meet tougher emission standards.
STEVEN A. KALOTA (The M.W. Kellogg Company):
In regard to swirl vanes of third stage separators, one of the other factors that will influence the performance or efficiency is the underflow flue gas flow rate. It can be neither too high nor too low. You can get re-entrainment or your cyclones will not be working very well. We have seen many instances of people cutting these rates down, crying to push more gas to their expander and, of course, they suffered performance loss. If you go too high, then you get re-entrainment. These things function best when there is a certain downward velocity. That, of course, is related to the disengaging area underneath these swirl tube assemblies. You do not want any gas-to-wall impingement coming out of these tubes either. So typically, I think, these underflow rates should be about 3 wt % of the total flue gas coming in.
QUESTION 12. 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, I have made a few simple estimates of thermal conversion and yield at typical catalyst temperatures prior to feed injection. For normal butane, thermal cracking
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58
completely without the influence of catalytic effects (which is a very simple chemistry to anticipate) at 1300F to 1350F and residence times on the order of 1/2 second to 1 second, conversion levels from 20% to 60% can be anticipated. One would expect the pyrolysis yield of the converted butane to be on the order of 2% hydrogen, 15% methane, 45% ethylene, 20% propylene, and the rest C4S and C5S, depending on the partial pressure in the system at the time. Obviously, it is a very bad idea to use butane as a lift gas as there is a lot of dry gas production.
ERNEST L. LEUENBERGER (ARC0 Products Company):
reduce the flue gas entrainment back to the reactor. When they turned the steam stripper off, they saw an increase of about ten numbers in ECAT microactivity. I am not sure if they quantified the amount of reduction in the gas entrainment they observed while the steam stripper was in service. Needless to say, the steam stripper has remained out of service.
ROSS:
I have some laboratory data that support Mr. Rosss calculations. We injected butane into a 1200F laboratory FCC riser reactor with a 2-second residence time. Butane conversion was 40%. The yields from the converted butane were 1 wt% hydrogen, 18 wt% methane, 24 wt% ethylene, 9 wt% ethane, 36 wt% propylene, 2 wt% propane, 1 wt% isobutane, 8 wt% butylenes, and 1 wt% coke. The differences between our product distribution and Mr. Rosss can be attributed to the hydrogen transfer activity of the FCC catalyst.
QUESTION 13. 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, including hopper and standpipe. In many cases, a unit has been expanded or the capacity simply increased without modifying the catalyst withdrawal system. The catalyst must enter the withdrawal system at a velocity lower than the bubble rise velocity to allow the catalyst to degas. The hopper cannot be too large, however, as this will result in excessive deaeration. Although tempting, steam stripping of the catalyst leaving the regenerator is not a good idea. The flue gas and inerts will be effectively removed; however, there is commercial precedent for excessive catalyst deactivation when stripping with steam at high temperature. In the standpipe, aeration is typically accomplished with air, this can be changed to steam, with the same caveat as above, or even fuel gas. One other note concerning other sources of inerts in the reactor, if you have air purged instruments in the reactor, replace them with steam or fuel gas.
STEVEN A. KALOTA (The M.W. Kellogg Company):
I have two stories on this, one operating and one mechanical. In the operating story, one refiner modified the aeration rates on the regenerator standpipe such that they operated between 90% and 115% of theoretical, compared to their previous operation where they were running about 130% to 140% of theoretical. In order to operate in this manner, all the aeration air orifice plates, which fed off of a single header to the standpipe, were replaced with individual aeration tap flow meters fed from a series of pressure-controlled headers. This allowed them to control accurately individual aeration rates so that the pressure profile would be as close to optimal as possible. 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. The amount of air actually transported to the reactor could be quantified in two ways. The first was from the amount of CO and CO2 measured in the absorber offgas stream. The second was by a proprietary design correlation that used catalyst circulation rate, catalyst flowing density, and catalyst skeletal density to correlate with the amount of gas entrained. 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. Were they really just interested in reducing inerts to the reactor, 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.
MARK SCHNAITH (UOP):
Unfortunately, if you want to maintain good catalyst circulation, you are going to have a certain amount of entrainment of inerts. Good standpipe design can help minimize, but never eliminate, this entrainment. However, we do have a potential solution in the works today. We have a new technology under development called the X design. In that technology is a mechanism by which we can remove the inerts from the regenerated catalyst before it enters the reactor.
QUESTION 14. 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?
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ROSS:
I hope you will bear with me. I will try to set the premise for some of the direct experience some of the other refiners on the panel may have. The industry is now well aware of the detrimental effects of post-riser cracking and product degradation, both catalytic and thermal. 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. Examples of these RTDs include closed or close coupled cyclones, vortex separator, and the Ramshorn Axial Cyclone licensed by Stone & Webster. 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. Start-up and operability factors are important aspects of these systems. When installing an advanced RTD, the amount of improvement is dependent on the type of separator replaced, the reactor temperature, and the amount of postriser residence time eliminated. Typical post-riser conversions of 4% to 5% are common with a residence time of about 20 seconds. In one case, as much as 10% post-riser conversion was measured resulting from a residence time of about 40 seconds. The improved performance noted after installing an RTD is a drop in dry gas production and an increase in valuable liquid products. The refiner then adjusts operating parameters to take advantage of the wet gas compressor capacity to drive the unit back to its limit, usually by increasing the riser temperature and reaping the benefits of higher LPG olefins and gasoline octane. In some instances, the gasoline yield may actually remain about the same even though overcracking would be expected at higher reactor temperature. In one case, we observed a drop in dry gas of more than 30%, in another a drop of about 20%, and in a third instance, an increase in feed rate of about l0%, made possible by the reduction in dry gas. The lost conversion when eliminating post-riser thermal conversion can be compensated for by increased catalyst-to-oil ratio, catalyst activity, riser temperature, or a combination ofall three. The most effective is an increase in catalyst-to-oil ratio which also results in an increase in yield selectivity. Another technology that reduces post-riser product degradation is the Amoco post-riser quench licensed by Stone & Webster. In this system, the product vapors are quenched after the catalyst has been removed or separated in a RTD. Typically 5% to 7% recycle of LCO (or similar refractory material) is injected just after vapor separation from the bulk of the catalyst. This results in cooling the product vapors by 50F to 70F 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 950F Thermal cracking is 60
effectively terminated in a low-cost, mechanically simple system, which requires no special operating procedures.
SOLIS:
In November the reactor of our Huelva Refinery Exxon FCCUs will be revamped to be retrofitted to Exxon short contact time technology. We have conducted extensive pilot plant work for catalyst screening, covering seven different catalysts. I have to say that the results have identified substantial performance differences between them. As a consequence, a proper catalyst selection is essential to get the benefits of the new technology.
VAN IDERSTINE:
Consumers Co-op has a 20,000 bbl/d UOP stack model FCCU, originally built in 1953. This summer we revamped the reactor with the UOP vortex separation device for riser termination and, at the same time, installed the UOP Optimix elevated radial feed nozzle arrangement. Combined, these changes have improved our yields. Prior to the revamp, we had a standard elephant trunk termination off the riser, and for the feed we had a UOP premix-type nozzle at the bottom of the Y piece. Since start-up, we have seen yield changes that have been as expected, or maybe slightly better. Gas make is down 25% to 30% for similar conditions. The LPG make is reduced by about 5%. The gasoline to heavy cycle oil yield is up approximately 3% to 4%, with the majority of that improvement occurring between the gasoline and the light cycle. Our slurry make increased slightly, as you would expect for less overcracking. One of the side benefits we realized as a result of not overcracking and less delta coke, was a reduction in regenerator temperature of about 50F. However, then by increasing the slurry recycle, we more than offset the initial increased slurry make. We can increase slurry recycle because we are not at the maximum capacity on the FCCU. The total cost of the revamp for the riser termination plus the feed nozzle arrangement was about $2.5 million. The payout should be within two years.
PARKER:
I am going to relate a recent experience from our Borger, Texas refinery. We have recently revamped both catalytic crackers at that facility. The first unit is an old Sinclair side-by-side cracker. We installed radial feed nozzles, an external cracking riser, and external rough-cut cyclones. We realized a dramatic reduction in the coke make on the unit and some reduction in the dry gas make. Following the start-up, we conducted a radioactive tracer study to evaluate the performance of the equipment. 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. From our instrumentation, etc.,
we believe the diplegs are sealed. So we are continuing to evaluate the cyclone performance in that area. The other unit is a Kellogg Model C cracker. That particular unit has plug valves inside the regenerator. The catalyst flows through the plug valves up through the riser. It has three internal risers. We installed nozzles on the plug valves using patented technology from Amoco and installed inertial separators on the end of the risers. That unit appears to be performing very well. We have not done tracer studies to determine the residence time or the separation efficiency.
ABRAHAMS:
around catalyst, quantify your mechanical changes, and then switch to the more active catalyst. Refiners concerned that they might not be able to circulate enough catalyst, or who are constrained in raising their reactor temperature, would probably be better off adding the more active catalyst before the revamp.
FRONDORF:
One of our plants experience with riser termination devices began in 1987 when rough-cut cyclones were installed. This allowed operating at slightly higher riser outlet temperatures and slightly more catalyst activity to replace thermal cracking with catalytic cracking. In 1995, this same unit was revamped to include a closed cyclone system, which further reduced thermal cracking as evidenced by lower coke and dry gas production. We went to higher riser temperatures, 1010F up to 1040F and higher matrix catalyst activity, from 70 MAT to 73 MAT The unit was revised to allow higher catalyst circulation to stay in heat balance; we went from 55 to 68 tons a minute. As further testimony to the old saying there is more than one way to skin a cat, this year we are revamping three FCCUs, one in each of our refineries. All of them are between 70,000 bbl/d and 90,000 bbl/d capacity, and we are using three different designs.
DEADY:
I want to add to Mr. Abrahams comments concerning the catalyst. Of all the operating changes that could be made, our preliminary work suggests that catalyst activity is probably preferred, and that the best yields are obtained if this is achieved with selective matrix activity. We have surveyed several refineries who did these types of revamps to determine the shifts they made in catalysts. As expected, most refiners increased equilibrium microactiviry rare earth level on the catalyst and total surface area to maintain conversion levels. Specifically, microactivity numbers increased by a range of 3 to 10 with the average being about 5 numbers. Rare earth levels increased an average of 7%, with a range of 0.4 wt % to 1.1 wt % rare earth on the catalyst. And the range of the total surface area increase was between 10 meters squared per gram and 40 meters squared per gram. A refiner recently asked us when refiners are going to these more active catalysts, before the revamp or after the revamp. There are basically two schools of thought on that. If you think you will be able to address the severity loss with increased reactor temperature and catalyst-to-oil ratio, then you can probably start up on the pre-turn-
At our Corpus Christi, Texas refinery, we have two UOP catalytic crackers, one a 1950 vintage, revamped stacked unit, the other a 1975 vintage side-by-side. We have not made any recent changes to riser termination at the Corpus Christi plant. The last one in 1987 involved an elephant trunk design. I guess that is self-explanatory. In general, the expectations for improved termination would be higher reactor temperature and/or catalyst activity to maintain the same conversion level. At the Lake Charles, Louisiana refinery, we have three 1944 vintage Kellogg Model 2 catalytic crackers. 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, depending on which FCCU we are discussing. We are initiating another set of revamps to move to full vertical risers, with external rough cut cyclones. The first unit is due to have its turnaround and revamp in the spring of next year. The current plan on that unit would be to increase catalyst activity to maintain conversion levels following the completion of the revamp. Ms. 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.
HANSEN:
We installed a close coupled cyclone system in October 1994. Dry gas, coke, and diolefin production have been reduced. We typically operated at maximum catalyst-tooil ratio and found that in addition to this, increasing catalyst activity by 2 to 4 MAT numbers and increasing riser temperature were needed to maintain conversion.
JOHNS:
Texaco has installed their negative pressure DirectCoupled Cyclone design at three locations: Port Arthur, Valero, and Nerefeco. Results from all three locations demonstrate significant reduction in dry gas make, higher oleficinity from less hydrogen transfer reactions at the low contact time, and substantially lower delta coke resulting in lower regenerator temperature (30F to 40F). Conversion level was maintained in all cases by increasing catalyst circulation and increasing the rare earth content of the catalyst to provide higher activity.
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GEORGE A. 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. Yields have been excellent and operations have been very robust over quite a wide range of operations. As contact time and therefore thermal cracking are reduced, other factors must be adjusted to maintain conversion and achieve optimum yield selectivities. The panel has already mentioned these factors; and we agree. They include catalyst activity, catalyst formulation, catalyst-to-oil ratio, and operating temperatures.
PAUL SESTILI (The M.W. Kellogg Company):
Not to belabor the point, but as you all know Kellogg offers Mobil closed cyclones as our improved riser termination device. To give you a quick summary of our recent experience, we have 19 units in operation that have been successfully running since 1985, about 100 years of cumulative operating experience, and about a million barrels a day in current operation.
ROBERT GLENDINNING (ABB Lumus Global, Inc.):
For anyone in the audience who may not be aware, Lummus currently licenses FCC technology with Texaco. It is interesting to note that in the Phillips Borger radiotracer study, a high dipleg vapor carryunder was detected with a positive pressure cyclone, despite sealing the dipleg in the stripper bed. This will in turn lead to higher hydrocarbon carryover rates to the regenerator. Our riser termination device, as Mr. Johns pointed out, is a negative pressure cyclone system that minimizes hydrocarbon carryover to the regenerator. When we actually look at the performance of the commercial units, what tends to happen relative to a positive pressure cyclone system, is a drop in regenerator temperature of 25F to 30F, which produces higher catalyst-to-oil ratios, increased conversion, and reduced dry gas production. So, whereas we agree that the riser termination device is important, we think the operating characteristics of the riser termination device are equally important. In a paper presented at the 1994 meeting of the Japan Petroleum Institute, we outlined the advantages of negative pressure direct coupled cyclones relative to positive pressure systems, and this has been clearly demonstrated by the observation of these substantial decreases in regenerator temperatures.
QUESTION 15. Excluding the effects of SOx reducing additives, 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. First of all, lower the excess O2. We know one refiner, an extreme case, who decreased his excess O2 from 6% to 2%, and eliminated a brown NOx plume. Managing promoter additions is also a key way to control the NOx. It is widely accepted that excess addition of standard CO promoters can increase FCC NOx emissions. Improving catalyst air distribution will also help with your NOx. Moving to a partial burn operation can help. However, sometimes the NOx from the CO boiler could still be a problem. You can also look at reducing the nitrogen in the feed by FCC feed hydrotreating, since increasing feed nitrogen has been correlated with increasing NOx emissions. We are investigating, in conjunction with a major oil company, additional additives that will reduce NOx by promoting the reaction between the NO and reductants such as CO or coke. Laboratory testing shows reductions of about 40% to 50% of NOx, and we expect to have a trial of this material by the end of the year. In addition, we will be conducting a commercial evaluation of a low NOx combustion promoter that has shown promise in the laboratory. This new combustion promoter has activity for CO combustion similar to that of conventional production promoters, but produces about 30% less NOx. Again, we are expecting a commercial trial of this material by the end of the year.
HANSEN:
Our operating permit limits the amount of NOx in the flue gas. The most effective method ofcontrol is operation at lower excess oxygen levels, such as 0.5%, and careful use of platinum-based combustion promoter. Afterburn can be a problem, especially at lower flue gas rates. There is a wet DeNOx process available. In this process the NO, which is typically the dominant species in NOx and insoluble in water, is converted to NO2 using sodium chlorite. The NO2 is then absorbed. A separate quench circuit is needed for this process because of the chemistry differences between NOx and SOx removals.
PARKER:
There have been reports in the literature on a correlation between basic nitrogen in the feed, and NOx. We tried to correlate that in our own plant because we run significant levels of basic nitrogen, in the 500 ppm to 1000 ppm range, and we could not correlate with the stack NOx. During stack testing, we did discover that if you have any ammonia or cyanide compounds in the flue gas from a quench or anything like that, it will show up as NOx on some of the stack tests.
G. ANDREW SMITH (INTERCAT Inc.)
Some of this question was also covered last year in the 1994 transcript. Refiners have the ability to reduce NOx 62
We have commercial experience in several units using a low NOx promoter. We have found that a combination
of a low-platinum promoter added at a constant platinum rate reduces NOx emissions and avoids afterburning.
PHILLIP NICCUM (The M. W. Kellogg Company):
Given the effect of combustion promoter and excess oxygen on NOx, units with good catalyst and air distribution, which can run at low excess oxygen with little or no combustion promoter, are going to show the best NOx performance. In addition, it has been found that the NOx is the result of nitrogen in the feedstock. Recent publications by W. R. Grace indicate that most of the nitrogen in the coke is converted into nitrogen gas in the regenerator, with some of the nitrogen emerging as NOx. 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, the spent catalyst is introduced evenly over the top of the regenerator bed; so there is a greater opportunity for the NOx to be reduced to nitrogen. The following chart shows the percent of the nitrogen in the coke that goes to NOx on the left side, and on the
bottom axis you have the percent oxygen in the flue gas. These are correlations of data from Mobil FCC units for three different types of regenerators. The top curve is the so-called swirl regenerator, which is a side entry dense bed regenerator. The curve in the center is a combustor type regenerator, and the lower curve is from the Kellogg Countercurrent Regenerator. You can see from the chart that the countercurrent regenerator provides a much lower percentage of the nitrogen in the coke going to NOx.
KING YEN YUNG (Akzo Nobel Chemicals BV):
My answer is in regard to the previous question about NOx reduction. I agree that a good way to achieve NOx reduction is through promoter management. In Europe, a refinery reduced the promoter addition by 40% and could reduce NOx by 50%. The penalty was increased afterburn to 40C. In a more recent example, we have an application that was using additive and they were suffering from afterburn, some 20C. They switched to a more effective promotion catalyst (INSITUPRO option). With this more effective promoter, they reduced the platinum on ECAT by 70%,
NOx from Commercial Regenerators
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decreased afterburn to 5C and achieved a NOx reduction of 30%.

QUESTION 16. Several SO x reduction technologies are available to the refiner (catalyst additives, scrubbers). 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, the operating cost would be about $9,000 a day with a capital cost ofabout $20 million. This is in order to achieve the new source performance standard requirement of 90% SO2 emissions reduction, or less than 50 ppm SO2 emissions. The standards with the flue gas scrubber are a little different, because of the new source performance standard requirements. We have not observed increased sulfur (or decreased sulfur, for that matter) in any of the liquid products with the SOx additive approach. All the sulfur recovered from the flue gas leaves the unit as H2S.
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. If the flue gas SOx level is less than 700 ppm to 900 ppm, assuming a requirement to reduce it to less than 300 ppm, the cost difference is about break-even. If the SOx level is higher than that, the lower operating cost of the scrubber will easily offset the higher initial capital investment. The scrubber investment is used as a credit for the electrostatic precipitator, which would not be necessary with the scrubber. Local economics may shift the break-even point, so it should be reviewed on a case-bycase basis. For existing units, I feel that unless a scrubber is in place, catalyst additives are the convenient solution. However, it should be realized that additives are not very active in partial combustion mode units. Again, additive efficiency and prices are highly variable, and cost-effectiveness tests in pilot plants are recommended. Regarding the second part of the question, the sulfur that is removed is SOx from the regenerator and is converted to H2S in the reactor. The catalyst additive has no significant effect on the sulfur distribution of the liquid products, but we have observed that some SOx catalyst additives can slightly reduce the sulfur in the FCC naphtha.
DEADY:
Our Corpus Christi, Texas refinery, operating on hydrotreated feed, does not have a flue gas scrubbing system. We use SOx reduction additive on an as-needed basis to meet final stack specifications. The Lake Charles, Louisiana refinery, operating on nonhydrotreated feed, uses SOx reduction additive on a regular basis to meet final stack specifications. 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. We have no plans at this time to install a flue gas scrubber. A spot reading from the Lake Charles plant for our SOx additive reduction would be about 35 cents per pound of SO2 removed. Neither refinery has seen a significant shift in sulfur content of the liquid products following SOx additive.
KELLER:
We are currently using an SOx reducing additive, which is effective in reducing the emissions to below our limit of 99 ppm. We currently add a 40-lb dosage (110 ton catalyst inventory), which lowers the SOx ppm about 20%. This reduction typically lasts from 4 to 16 hours. We have not seen any significant shifts in the sulfur content of the liquid products with the use of the additive.
ROSS:
I agree with Mr. Solis, especially on his point that the break-even point is highly unit-specific. We found that it is unit-specific because the SOx capture efficiency of SOx reducing additives such as DeSox is extremely unitspecific. Based upon our experience, we see a slightly higher break-even point with DeSox technology. We see that the SOx reducing additives are most cost-effective if you have SOx emissions below 2500 ppm base. Above about 3000 ppm base SOx, the flue gas scrubbing economics can become much more attractive. In general, because this is so unit-specific, we would recommend a commercial trial of SOx reducing additive just to quantify that performance. As an example, the cost for the additive approach to reduce SOx from about 600 ppm to about 300 ppm is about $4,000 a day for a typical 50,000 bbl/d unit, with an additional capital cost of about $50,000 for a loading system. 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. In some of the analyses we have done, it suggested somewhat less than 1500 ppm and perhaps closer to the 1000 number we heard before. Regarding its effectiveness in partial combustion, we have seen trials measuring an effectiveness of 50% to 70% in the first stage partial combustion regenerator of a twostage regeneration resid unit. Each SOx reduction technology has advantages and disadvantages which are site-specific. Issues to be addressed include the following: Required reduction in SOx emissions Capital cost Operating and maintenance 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, solids disposal, opacity Plot space requirements
PAUL SESTILI (The M. W. Kellogg Company):
Kellogg Comparison Of Pollution Control Options
To determine the most applicable technology for pollution control in a refinery, an overall analysis of the benefits of each system must be made. Kellogg recently completed a study comparing a wet gas scrubber to a SO, reduction catalyst plus electrostatic precipitator. The wet gas scrubber tends to have a higher capital investment, but lower maintenance costs and operator attention. The overall plot space requirement for the scrubber is higher; however, the purge treatment unit can be placed off-site. As a result, the on-site plot space requirement is much lower for the scrubber. The catalyst plus precipitator option has a lower capital cost, but requires more maintenance and operator attention due to the ESP. The waste disposal for the scrubber is both solid and liquid, whereas the ESP waste is a solid dust only. In summary, it is important to look at the big picture when determining the most applicable pollution control system for a given refinery. See following table.
With the recent improvements in SOx additives, refineries have a choice of purchasing an additive with equivalent performance to current deSOx additives that cost 40% less, or purchasing ones with 40% greater pickup efficiencies at similar pricing. We would also advise refiners that are considering their options to run a short test with a SOx additive, like the NO-SOx family, to determine their economics. 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.
VICENTE A. 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. The only thing that I would like to add is that scrubbing, such as the Exxon Wet Gas Scrubber System, is really the only option that controls both SO x and particulates in one single unit. 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
emissions standards for FCC feeds with up to 3% sulfur, and can simultaneously meet the U.S. particulate removal specification of 1 lb per thousand pounds of coke burned, or 50 mg per normal cubic meter, which is frequently specified abroad.
MORGAN:
JOHNS:
Once a scrubber has been approved by a state, your operating permit requires that the scrubber be in service. For that reason, if your scrubber has a malfunction, you may find it necessary to shut down your FCCU. From an operating standpoint, that, to me, greatly favors the deSOx type operation.
THOMAS WALKER (Belco Technologies Corporation):
For this response I would like to relate an experience I had on a unit several years back. This unit had continuous catalyst additions, and we tried continuous withdrawal for several months with no noticeable effects. I suppose we were lucky at this, but there should be no difference if you are withdrawing from a location that preferentially removes the older, larger, aged particles of catalyst in either continuous or non-continuous mode.
ROSS:
Belco, in association with a New Jersey refinery, completed a study in regard to catalyst additive and scrubber options for deSOx Obviously, many environmental, process, and economic variables play an important role as mentioned by several of the people. However, I would like to state that, at this time, that refinery had opted for the Belco EDV scrubber, and a review of the studys content and decision process can be found in a paper compiled by Belco entitled Flue Gas Cleaning on Fluid Catalytic Cracking. Please contact Belco at the address below to obtain a copy of this paper. 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. Again, this paper reviews Valeros decision and operating experience with the Belco EDV. VICENTE A. CITARELLA (Exxon Research & Engineering Company): With respect to the need to shut down an FCCU because of a scrubber malfunction, 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.
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. 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. Generally speaking, 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. Continuous addition is considered best practice as the catalyst activity level is maintained at a nearly constant level. Adedicated line is typically provided for this purpose and should not interfere with withdrawal operations. For residue cracking operations, 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. Continuous addition also levels out the catalyst loss associated with fresh addition to avoid peaks in catalyst loss.
SOLIS:
Regarding flue gas scrubbers being part of the operating permit, per Mr. Morgans comment, ESPs are part of the operating permit where we live, too.
QUESTION 17. We have moved from once-a-day to continuous FCC catalyst addition. Due to common lines, we have to shut this system down periodically to make batch withdrawals. 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, large batches of catalyst addition. The spike of fresh catalyst activity can result in a short-term overcracking situation with an increase in coke and gas products. These product increases can be seen in the main column and gas concentration facilities and the disturbances prevent continuous operation at the highest throughput. Catalyst withdrawal is usually done on a batch basis since it does not change the composition of the ECAT inventory, and no process performance issues are seen. As long as the time for withdrawal is relatively short, say 1 to 2 hours, it is unlikely that an interruption in fresh catalyst addition will be seen. In RCC units, where catalyst addition is quite large, withdrawals are made on a daily basis. In this case, there is a continuous withdrawal system, but its purpose is mainly to cool the withdrawn catalyst so it can safely be sent to the storage hopper.
There is a large RCC unit in the Far East operating with a continuous catalyst withdrawal system, fully automated,
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that can operate at rates of 30 tons per day withdrawal. The high rate is necessary to control metals levels on the equilibrium catalyst. In a system like this, one key is to have an effective cooling system to avoid overheating the storage hopper. This system has been in operation for more than one year.
STEPHEN J. YANIK (Akzo Nobel Chemicals Inc.):
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. It has a couple of benefits. It gives you more fresh catalyst inventory and also gives you some flexibility in possibly blending a couple of catalysts. So, having two fresh catalyst silos is becoming rather common on those big residual cracking units.
QUESTION 18. 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, and all of those tested were unsatisfactory. While the removal rates were very good, the systems were plagued with poor operability and inability to adequately backflush the fine material from the pores of the filter media. These difficulties made these systems extremely unpopular with the operations personnel, and, in addition, maintenance was high. Since then, they have not tried these filters again.
ROSS:
We currently operate a Gulftronics filtration system for our slurry, which reduces catalyst content of the slurry from 0.2% ash to a clarified slurry oil product with 0.005% ash. We have had very few maintenance problems with the system to date. 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. 6 fuel stream, but the content of the ash was too high and would have brought the fuel oil off specification. Backflushing to the riser does create unique problems with control on your FCCU, and that is a constant problem for us as far as cycling the unit is concerned. Bight now that is the best place that we have found to put the material.
ABRAHAMS:
One of our plants used a porous metal filtration system on its slurry oil. The backflush material was sent to the riser and caused opacity problems since the stack was the only place for fines to go. The unit is not equipped with an electrostatic precipitator. As a result, the filter system was removed from service and moved to another location. Our suggestion for disposal of backflush in this situation is to send it to a coker if possible. As a contrast to what Mr. Emanuel was saying a minute ago, we had a Gulftronics filtration system in one of our refineries, and we got rid of it.
One resid unit that I am aware of used the sintered mesh filtering system with excellent results over three years, and a new unit about to start up will use the same system. A cake of catalyst builds up, forming on the filter with the cut point on particle size typically between 10 to 20 microns. Periodically, the cake must be removed by backflushing into the FCC riser to limit pressure drop. 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. 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. Efficiency is very good with virtual exclusion of particles greater than about 15 microns. The oil retained on the captured catalyst is recycled back to the riser with the backflush. A typical product oil stream will contain about 50 ppm catalyst or less. Control of the filter size/efficiency is important if the material is to be recycled to the riser. 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. 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. A finer filtration will likely require disposal means other than recycle. Another refiner we are aware of has experience with both the sintered mesh and filter systems. When a sintered metal filter is used without dependence on the cake, the elements must be periodically cleaned off-line, as well as periodically backflushed. Disposal is typically limited to the FCC riser, coker, or asphalt, if specifications allow.
SIM ROMERO (BP Oil):
We have two sintered metal filters in Ohio. The first filter was commissioned about 5 years ago and is not currently in service. The second filter has been in service for the last 3 years and is operating with little to no problems. The key to the operations was the location of the filter. The first filter was located in the tank farm with
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feed at 300F. to 350F too cold. This filter had plugging problems and required frequent cleaning (about every 3 to 6 months). The other filter was located at the unit and had a much hotter feed. The hot feed reduced the plugging in the filter. The filter has been in operation for 3 years and has been cleaned only once.
ROBERT L. BROWN (Pall Process Filtration Co.):
Pall Rigimesh backwash systems are now being commercially used in refineries throughout the world. To date, there have been twelve systems sold, and there are currently four in operation. The oldest has been in operation for over 3 years with minimal maintenance problems. 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, and in all cases the backwash fluid is designed to go back to the riser. The quantity or the volume of the backwash fluid is typically less than 2% of the amount of slurry oil that is being processed.
STEVEN A. KALOTA (The M. W. Kellogg Company):
The third case involves the high pressure absorber tower. This is for a grassroots plant, and our studies show that a higher pressure absorber tower is actually more economical than the cryogenic system. In this case, the absorber tower runs about 260 psi and the propylene recovery is 92%. We also did a process study for a low pressure FCC gas plant. In this case the gas plant absorber was limited to 140 psi operating pressure. We used refrigeration to cool the naphtha for the absorber and the lean oil for the sponge absorber. Because the gas and the oil contain moisture, we had to watch hydrates formation. It limited the temperature on the top of the absorber to no lower than 60F. The result showed increased propylene recovery from 81% to 89%.
SOLIS:
In fairness to everybody who makes slurry separators, thereare other alternatives: liquid cyclones or hydrocyclones made by Dorr Oliver or Vortoil. The etched dish and Gulftronics are very good if you need to get a very low solids concentration. But if you are looking for concentrations just under 500 ppm, then one of these liquid cyclones is a good alternative that is not quite as expensive or as maintenance-unfriendly.
QUESTION 19. Propylene recovery from the Gas Concentration Unit is a concern. 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. So it is difficult to compare one case to another because often they are not on the same yield basis. We have seen refineries improve the propylene recovery through various methods. The first is a combination of increased lean oil circulation and adding trays to the de-ethanizer absorber tower. One data point we had for a 175 psig absorber system showed an increase in the propylene recovery from 79% to 87%. The second approach is the addition of a cryogenic unit for the tail gas. At least one refinery we know of, after installing the cryogenic unit, shut down the sponge oil absorber altogether. The numbers we have in this case are from 81% to 90% recovery. 68
We have a conventional absorption and stripping section and a high-efficiency fractionation system to recover and purify propylene. The role of the absorption and stripping section is to remove C2, H2S and, COS. Our propylene recovery in this section is 93%. The fractionation system consists of a high performer propane-propylene splitter (see Petrochemical Processing Session, Question 1) to separate propane from propylene. We have a loss of 5% of propylene in the propane bottom stream. Downstream of this splitter we have a molecular sieve treater to remove the traces of COS. Ofconcern in propane/propylene splitters is the potential buildup of trace contaminants in the column. In particular, methyl acetylene and propadiene, when present in trace quantities in the column feed, have volatilities between those of propane and propylene. Thus, these components do not readily leave the column with the overhead or bottoms product. Rather, they tend to build up in large quantities in the middle trays of the column. Generally, the presence of these components in the column does not affect column performance or product quality. However, when the column is upset, potentially a large quantity of methyl acetylene or propadiene could leave the column with either the overhead or bottom product, causing either stream to go off-specification.
PARKER:
At our Borger, Texas refinery we replaced trays with packing in the top three trays and the bottom twelve trays in the lean oil absorber. We believe it was successful. I do not have the efficiency gain numbers, but the current recovery percent is in the mid-90s. On our newest catalytic cracker at Sweeny, Texas, we handle this somewhat differently. The overhead vapor out of the lean oil absorber is combined with the lean oil prior to the lean oil cooler, and then goes to a separation drum, with lean oil pumped from the separation drum to the absorber. There is probably a name for this, but I do not know it. Our
recovery there runs about 3% propylene in the offgas during the summer months.
ROSS:
A new lean oil system with sponge absorber will recover about 93% to 95% of the propylene, with losses to the offgas system. A common step to improve the efficiency is to chill the lean oil to about 50F resulting in about a 95% to 97% recovery. A more effective and economical approach than increased lean oil circulation is the addition of a cryogenic recovery system, which may include turbo expansion and/or refrigeration. If ethylene recovery is also desired due to the proximity to a petrochemical complex, a selfrefluxing dephlegmator exchanger-based system should be considered. An example of this type of system can be found at Mobils Beaumont, Texas facility, which has been in operation since 1987 processing FCC offgas with a simple payback of 11 months. Any of these cryogenic systems will recover essentially all of the propylene.
EMANUEL:
reducing the absorption oil temperature, increasing the intercooler duties and increasing C2 s that might be allowed in the alkylation unit feed. With chilling and improved process designs, recoveries to 98%+ are possible within the unit. Sponge oil (typically LCO) has little effect on C3 recovery in the primary absorber unless C3 recovery is poor. Absorber efficiency has little impact on C3 recovery unless the column is flooded. The stripper (or de-ethanizer) performance can have a significant impact on recovery, especially if the absorber is stacked on the stripper (no recycle to the high pressure receiver condenser). Once the existing process has been optimized, the process and equipment designs that should be looked at include chilled lean oil and main fractionator overhead liquid, chilled intercoolers, presaturator, and process control issues. Stand-alone refrigerated propylene recovery units have been used with varying degrees of success. From what we have seen, the major concern for these units is including sufficient flexibility to maintain recoveries over a reasonable operating yield range.
DELBERT F. TOLEN (Rocky Mountain Salvage & Equip.):
In addition to cryogenic-type processes, we are beginning to look at a new process that uses ultra high pressure lean oil absorption. The system is based on a typical lean oil design, which can be found in your FCC unit, but it is designed to operate at high pressures with a proprietary lean oil. The company currently marketing this process is Advanced Extraction Technologies, Inc.
FRONDORF:
Our Corpus Christi refinery operates with a primary and a sponge absorber system, similar to what has previously been mentioned, with cooling water for heat removal. We see a recovery efficiency of around 93% on that system. At the Lake Charles refinery, we operate with a primary absorber only with a chilled lean oil system, approximately GOOF, and see normal recovery efficiencies approaching 95%.
KELLER:
Typical propylene recoveries from gas conservation units are from 92% to 95%. They principally depend on the pressure and how you run your stripper to strip the H2S. Twenty-five years ago we built a refrigerated gas absorption plant in a 20,000 bbl/d refinery to recover the propylene and butylene. The payout on that operation was about nine months. So, the economics are very clear cut on installing refrigerated gas absorption.
REZA SAOEGHBEIGI (RMS Engineering, Inc.):
Another option to improve the C3 /C4 recovery is to install a presaturated drum. This drum will use the cooled debutanized gasoline as the lean oil. We have seen recovery improvement anywhere from 3% to 5%.
QUESTION 20. What is the preferred contact time between catalyst and oil, upstream of a primary separation device, to minimize the production of dry gas and achieve maximum conversion? ROSS:
We currently recover about 92 wt % of the C3=. We have a UOP Gas Concentration Unit, which uses a primary absorber to absorb 91.6% of the C3s and almost all of the C4s out of the fuel gas. Debutanizer bottoms is the lean oil at the top, and main column overhead liquid is fed 10 trays down in our 40-tray primary absorber.
ANDREW SLOLEY (Process Consulting Services Inc.):
Increased propylene production more than proportionally increases losses at any given concentration unit. Recoveries in the range of 92% to 95% can be considered current good performance. Improving yields from below 90% to this range is usually straightforward and includes maximized absorber pressure to the compressor limits,
There are several distinct zones in the FCC riser: catalyst/fied mixing, feed vaporization, riser vapor phase catalytic cracking, product vapor, and catalyst separation. 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, mixing, and vaporization are nearly ideal. At constant conversion, the catalyst circulation rate must increase from about 6 to 7.5 and the riser
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temperature increase from 980F to about 1000F when the residence time-is reduced from 1.6 seconds (conventional) to 0.4 seconds based on outlet moles. The gasoline yield increases by about 3 wt % to 4 wt % with the selectivity increased by several points, at the same conversion. The improvement comes largely at the expense of LPG, but the dry gas is also reduced by more than 20% as a result of the reduced time, higher catalyst-to-oil ratio, and lower regenerator temperature. These results were obtained using conventional catalyst withdrawn from a commercial unit, and therefore the catalyst was not an optimized formulation for short residence operation. In order to obtain the reduction in residence time to about 0.5 seconds in the riser vapor phase cracking section, a very efficient feed injection and catalyst mixing/contacting system is required. The order of magnitude of time required for vaporization is 0.1 seconds and becomes a significant part of the total residence time. 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. This type of performance will be required to realize the benefits of ultra short residence time. Another consideration of short residence time systems is that of product quench. The rapid end of riser separation techniques used today will be inadequate. Just as the ethylene industry moved from simple mechanical layout designs to control residence time to quench fluid injection to freeze degradation reactions, the refining industry will likely move this way as well. VAN IDERSTINE: Historically, the conventional residence time in risers has been on the order of 1 to 3 seconds. We are currently at a 2.3 second residence at 17,500 bbl/d after our revamp. The optimum residence time for each refiner depends on what their hardware configuration is, and what their conversion objectives are.
JOHNS:
TUAN NGUYEN (The M. W. Kellogg Company):
The optimum contact time between catalyst and oil in the riser depends on several factors: the type of feed being processed, the type of catalyst being used, 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, higher riser outlet temperature, and shorter riser residence time in order to maximize conversion while minimizing the over-cracking of gasoline to LPG and dry gas. At the M. W. Kellogg Technology Development Center, we have conducted a number of FCC pilot plant experiments to look at very short contact time cracking. So, we have seen little or no advantage for going to ultra short contact time cracking. 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, diffusion of these high molecular weight feed molecules into the active sites on the catalyst, cracking the feed to product, and diffusion of the hydrocarbon products out of the catalyst.
We need to keep in mind an important principle with regard to residence time. As you reduce the total system residence time in the reactor, you can improve your yield selectivity dramatically. Of course, what you give up is some conversion of that feedstock. A severity increase is required to gain back conversion, and some of the selectivity gains can be lost. Although traditional riser systems have operated in the 2 to 3 second range, the goal of the modern systems today is to reduce that residence or contact time without losing a substantial amount of conversion. One such system, the BAR-CO MSCC process, eliminates the reactor riser and features an ultra short contact time while maintaining effective conversion. Low dry gas and good gasoline selectivity have been demonstrated in two commercial installations. In May 1995, UOP and BAR-CO signed an agreement that gives UOP exclusive licensing rights for the MSCC technology. In June 1995, UOP licensed a 100 mbpd MSCC unit in the U.S., which is currently in design and construction.
DELBERT F. TOLEN (Rocky Mountain Salvage & Equipment Co.):
For the direct coupled system previously discussed, at Texaco we design for maximum conversion with minimum gas make and a contact time of 1.5 to 2 seconds. This is dependent on paraffin content and carbon residue in the charge.
I am sure Mr. Dave Bartholic of BAR-CO is pleased with Mr. Rosss remark about 0.4 seconds, since the MSCC design is about 0.001 seconds; the preferred time is between 0.001 and 3, and is feedstock dependent.
I continually hear extremely low numbers for preferred contact times. As I remember chemical thermodynamics, the reaction rate is proportional to the contact time times the temperature, and as 1 see it, 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. My observation of a unit with extremely short contact time was that once they reached a conversion level of about 78, very little of the diesel boiling range material in the
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feed was converted. It almost totally goes through unconverted. This unit made light cycle oil of 36 cetane number, which says the diesel fuel went through untracked. Almost all of the bottoms was cracked in that short contact unit. It only made 3% slurry with a 1% carbon residue feed. So it simply says, yes, all the heavy oil can be cracked in a very short contact time. But when you want to crack something in a 650F to 750F boiling range, you are going to have to increase contact time or increase temperature. The unit I am referring to ran at 1025F reactor temperature. So how high do we have to go to convert diesel boiling range in a catalytic cracker?
QUESTION 21. 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, which would you choose? VAN IDERSTINE:
roughly half of the above, but typically have a project payback measured in months. When differentiating between feed injection and riser termination the distinction between the two must be appreciated. Feed injection creates the yield pattern that riser termination seeks to maintain. Once one has optimized the feed injection system, the focus should be riser termination as there is no point in preserving an inferior yield.
SHEN:
I agree with all the panelists comments that, all other things being equal, we would choose the radial feed nozzles over riser termination devices. When I asked this question to one of our process engineers who holds two riser termination device design patents, he selected the feed nozzle over the riser termination device.
HANSEN:
This is one of those it depends responses. It depends on what you are changing from. In our particular case, we chose to change both feed nozzles and termination devices at the same time. It would have been nice to change one and then the other, and then evaluate both of them; but we thought, to obtain the maximum benefit, we would do them both at the same time. The one thing I can say though, is that the riser termination in the reactors is going to be more expensive. In our case, we spent $2.5 million total for both of the changes, and the riser termination change to the vortex separator was probably 50% more costly than the feed nozzle revamp. Again, you must examine your situation. Ask yourself what your configuration is today, what you want to change to, and what your process objectives are. Then apply your own economics.
MORGAN:
Valero chose to install both improved feed nozzles and close coupled cyclones in the unit. The improved feed nozzles were installed in 1989, and a close coupled cyclone system was installed in 1994. Installation of the new feed nozzles did result in improved yields, but we are not sure if improved coke make was fully realized. Installation of the close coupled cyclone system resulted in reduced dry gas, coke, and diolefin production. It is difficult to quantify the relative economics of these two items as other unit changes impacted unit yield patterns, feed rate and feed composition, were made at the same time.
KELLER:
Yes, we recently completed a study to determine what would give us the best return on our investment, as I am sure everyone else is, we are also very tight on capital. Our answer to that question was clearly the feed nozzles give you the greatest return on your investment, and we chose to delay doing any work with riser termination devices until a later time.
ROSS:
Ideally we would like to install both upgrades to our unit. If we had to choose one step first, we would select the high pressure radial feed nozzles on the reactor riser over a modern riser termination. The feed nozzles are a quicker, lower cost upgrade to the unit. A new feed system would cost on the order of $l.5 million and would provide better selectivity and an estimated 4% increase in conversion. 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. The riser termination would increase conversion by minimizing coke, which would allow more catalyst circulation. If we installed the modern riser termination without other modifications, we would be limited on catalyst circulation and minimum coke make.
Stone & Webster and other licensors have converted many axial feed injection systems to radial injection systems with dramatic results. Typically, the dry gas reduces by 20% relative, the gasoline increases by about 5% absolute or more, and the coke selectivity is improved, allowing even further yield gains. Improvements when changing from one radial feed injection system to another are
I am glad to hear the panel agrees with me. There is no doubt in my mind that if you must take one or the other, you take feed nozzles. They are faster and cheaper, and radial nozzles can give you excellent results. We had the luxury of only installing nozzles when we were looking at both nozzles and riser termination. But we just put in the 71
nozzles, and the subsequent yields destroyed any further payout for installing the extensive, expensive riser termination design(s). It is good, radial feed nozzles all the way.
DELBERT F. TOLEN (Rocky Mountain Salvage & Equip.):
DEADY:
I agree that feed nozzles are far more important than termination devices. The speed of mixing the oil and catalyst is most important.
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). If you change out a RTD for a short contact time (SCT) RTD, without first modifying the feed nozzles (e.g., keep old-style shower head nozzles or open pipe systems), you will coke the reactor transfer line. Two of our competitors refineries in Europe installed direct coupled cyclones (DCC) and kept their existing shower head feed nozzles. The refineries had to shut down within the year due to coke buildup in the reactor transfer line (RTL). They were basically not vaporizing and cracking the feedstock in the riser, thus condensing the reaction vapors in the RTL as coke precursor liquid. This did not occur prior to SCT RTD installation, as the reactor vapors leaving the riser spent a long time in the reactor disengaging vessel where they cracked further. Thus, only stable reaction vapors passed into the RTL.
Going from an axial feed injection system to a radial feed injection system will pay out in almost every case. 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. There are several things that come into play. For a unit with a very large disengager, the payout is going to be higher. For a unit where the product slate and the capacity allow operation at very high temperatures, the payout is going to be higher for a closed cyclone system. And also, if you are starting with an inertial separator device, rather than a more efficient riser cyclone, the payout is going to be higher. So the payout for the closed cyclone system is more variable. REZA SADEGHBEIGI (RMS Engineering, Inc.): 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 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.
QUESTION 22. 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, decreasing catalyst-to-oil ratio, decreasing gasoline end point, and increasing naphtha recycle. The most common option that refiners appear to be doing today is lowering the gasoline cut point. For example, from some ofour pilot plant data, we see that lowering the cut point from a T90 of about 380F to about 300F reduces the gasoline sulfur by about 40%, and also reduces the gasoline volume by about 15 vol%. The impact on RON is variable and will depend on the specific boiling point curve of the gasoline, i.e., the shape of the gasoline boiling point curve for each refiner. Since each refiner has a unique gasoline boiling point curve, the only way to quantify the octane change is to look at the actual distillation. Also related to changing cut point, refiners should make sure that their column operation is well controlled so that there is good control in the gasoline end point. If a refiner has a sloppy cut or the end point fluctuates, the gasoline sulfur can also fluctuate greatly and changing the cut point might not have as great an effect on reducing the gasoline sulfur. Regarding the other variables, we have laboratory data that show that decreasing reactor temperature by about 40F decreases the sulfur in gasoline by about 7% and decreases octane about 1.5 numbers. Decreasing the catalyst-to-oil ratio will also decrease the gasoline sulfur and RON. These changes were reported in the 1993 NPRA paper number AM-93-55. Neither of these, lowering reactor temperature or changing catalyst-to-oil ratio, is a very satisfactory way of reducing sulfur while maintaining gasoline octanes. 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. In the 1994 transcripts feed hydrotreating and product hydrotreating were also discussed as options.
EMANUEL:
We feel, of course, 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. In our particular stream, the heaviest 10% of the heavy FCC naphtha contains about 30% of the sulfur in the whole stream. Right now we are moving that cut point around as the conventional gasoline limits dictate.
SOLIS:
The sulfur distribution in the products is largely controlled by sulfur in the feed. At a given conversion level, assuming maximum gasoline product is desired, there is not much control over the gasoline sulfur. If there is room
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to reduce the gasoline boiling range, a significant amount of sulfur can be moved into the LCO product. Typically about 50% of the sulfur in gasoline boils between 380F and 430F This can be an octane rich portion of the gasoline, however, and eliminating it from the gasoline product can have an impact on octane. Catalyst manufacturers have tested formulations that will reduce the sulfur in gasoline. This work is still in its early days, but the principle has been demonstrated in commercial trials. This route appears to have more sulfur-reducing potential for the front end of the gasoline, whereas the end point distillation change reduces the back end sulfur. Finally, there have been announced several processes for downstream of the FCC, which will remove sulfur from the gasoline product with minimum reduction of octane.
QUESTION 23. In fluid catalytic cracking units practicing riser lift gas technology, what is the preferred operating procedure when lower quality feed causes an increase in the yield of fight gases? In units with lift gas, processing high metals feedstocks, 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.
QUESTION 24. 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. 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, and I only found one refiner. They reported their experience in the 1994 transcript. In it, they reported antimony-to-nickel ratios on the order of 0.15 to 0.2, compared to the more typical FCC operations on the order of 0.25 to 0.3 antimony-tonickel. The implication is that the lift gas is doing some of the passivation, and the antimony is doing additional passivation. This has not been quantified, but I suspect that the effects are somewhat additive. Another refiner who uses lift gases is also usingacatalyst that contains a nickel passivating matrix. Their hydrogen dropped when they switched from their previous catalyst to their current catalyst, indicating that the use of a metals passivation matrix also provides benefits over and above those obtained from lift gas.
EMANUEL:
We currently use lift gas in our UOP FCCU. We do not use antimony. During situations of increased yield of light gases to the point where we are wet gas compressor limited, we have reduced the lift gas to the riser. In some cases in the summertime, we have removed lift gas completely to try to maintain FCC feed rates. We typically run with a nickel plus vanadium in the neighborhood of 2000 ppm to 2500 ppm.
We are aware of two rules of thumb concerning how much washwater should be used on an FCCU. One says 2 gpm/l000 bbl of feed is adequate. The other one says 1 gpm/1000 bbl of feed is adequate. Having said that, I have to tell you that we are not comfortable with either one of them. These obviously are predicated on the fact that there are certain operating conditions on a unit, but not all units operate under the same conditions. 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, we can create a situation where there will be serious erosion/corrosion; that actually would be a worse problem to deal with than if we did not have a water wash in the system. Conversely, if too little water is added in the overhead, since normally main fractionator overhead water is recirculated in this situation, 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. That also will cause an extremely serious corrosive environment. The flow of the washwater is extremely important. People have used two different schemes: one is counter current, the other co-current. Counter current typically has achieved mixed results. We suggest that people go with the co-current flow whereby the flow goes from main fractionator overhead, to first stage after cooler, to second stage after cooler. The next part of the question deals with washwater sources. As I said earlier, the most commonly used source is main fractionator overhead water. We have also seen stripped sour water used successfully as a washwater. Where people have extremely high cyanide levels or a serious problem with hydrogen blistering, they have actually gone to the extent of using boiler feedwater. On the last part of the question, our feeling is that even if the feed is hydrotreated, it is not appropriate to reduce the amount of washwater that is used on the overhead. If the calculation was done correctly, and keeping in mind that you are trying to both dilute cyanides and remove some of the solids from the system, then the same amount of washwater is required.
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SHEN:
I agree with most of the comments Mr. Potscavage made, and I want to emphasize that we agree co-current is better than counter current in the flow arrangement. On the topic of the water quality, I have one comment. When you inject polysulfide material into the water for cyanide control, it is important that the water have a high conductivity level to ensure the polysulfides will suspend in the washwater. Because of this, we feel that the stripped sour water is a very good resource. Steam condensate is not only more expensive, it may also be low in conductivity. An article published by NACE can be used as good reference: NACE Paper, No. 206, Carbonate Stress Corrosion Cracking of Carbon Steel in Refinery FCC Main Fractionator Overheat Systems, April 1990.
ROSS:
Pertaining to the third part of the question, we just commissioned a high pressure hydrotreater ahead of the FCC. We did not change our washwater rate, but that did allow us to trim back considerably on the polysulfide use. We monitor with the spot test for cyanides using iodine and starch solutions, making sure that it stays negative.
PAUL FEARNSIDE (Nalco/Exxon Energy Chemical Company):
We are finding it is not so much a question of how much washwater, but how that washwater is contacted against the flowing gas stream. 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, you are just not going to do the proper job, regardless of the washwater flow rate.
QUESTION 25. 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. Potscavage. 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. Although a total washwater rate of about 1 gpm to 2 gpm/l000 bbl/d of feed is typically reported, the makeup is often unclear fresh or recycle sour water. The makeup of this recycle water depends on the amount of fresh water entering the overhead system as reactor steam (dispersion steam, stripping steam, etc.). If the FCC is a resid unit, the total reaction system steam rate can approach the total 1 gpm to 2 gpm, thereby allowing for only intermittent or infrequent use of additional fresh water injection. For a gas oil cracker, over half of the total water recycled may be fresh, i.e., not coming from the reactor. Approximately 0.5 gpm to 1.0 gpm of sour water per 1000 bbl/d of feed is typically recycled to the overhead line on a continuous, but sometimes intermittent, basis. As noted, 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. At the WGC interstage cooler, 1 gpm to 2 gpm of sour water is injected per 1000 bbl/d of feed and collected for injection into the high- pressure receiver where it is collected and directed to the sour water stripper.
KELLER:
As unit capacities are pushed to the limit, usually air blower or wet gas compressor limitations bottleneck the unit, not catalyst circulation limitations. Most UOP FCC units run to other limits before catalyst circulation limits are reached. The ultimate standpipe circulation limit will depend on catalyst entry condition and physical properties, standpipe angle, configuration, and length. Many units run up to 900,000 1b/sq ft/hr with some approaching l,000,000 1b/sq ft/hr. The reactor stripper will circulate everything the standpipe can handle since it is larger, but stripping performance will deteriorate as flux rates over design are used. The usual remedy for an over-fluxed stripper is to increase the stripping steam rate to try to improve its performance. Eventually, the combination of the high catalyst flux and high steam rate can result in a catalyst flow stoppage in the stripper.
ROSS:
We follow UOPs recommendation of 2 gpm/ 1000 bbl of feedstock. We use cold condensate which also has a corrosion inhibitor injected to lay down a corrosion barrier. The cold condensate is monitored for excessive oxygen content, less than 100 ppb. Cyanide production is a function of Total N in the feed, nitrogen type, and reactor operating conditions.
Standpipe velocity and flux rate limits are somewhat subjective. In a long, well aerated, vertical standpipe with a good catalyst hopper design, a flux rate of 275 1b/sec/sq ft to 300 1b/sec/sq ft has been demonstrated. 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. In some bend, slanted, or U-bend configurations, the higher flux and velocity are actually preferred to reduce the time for deaeration in the nonvertical section of the standpipe. 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, depending on the catalyst properties, is a difficult transition zone where bubbles in the standpipe tend to stagnate the catalyst velocity equals the bubble
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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. Below this flux, the flow becomes extremely stable again as the flow is now dense or pack flow. The only problem is that very large line sizes must be used if one designs at this flux rate. As for catalyst strippers, typical flux rates of 600 1b/min/sq ft to 1200 1b/min/sq ft have demonstrated good performance. The flux rate indirectly reflects stripper residence time and vapor-catalyst relative velocity. A flux as high as 1500 1b/min/sq ft has been encountered, but the performance was fairly poor as measured by high hydrogen in coke values. A theoretical choke condition can be calculated at fluxes above about 1200 1b/min/sq ft depending on the baffle spacing.
I would like to discuss some experiences related to annular strippers, which typically have a riser running up through the center of the stripper. 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 there is excessive entrainment of hydrocarbons to the regenerator or, if you will, a poor stripping efficiency. The curves on the graph below show, on the left, the stripper efficiency versus the mass flux rate. At a certain point the efficiency falls. The curve on the right is the density curve, and it also falls at a high mass flux rate and is falling because of the entrainment of the gas down the stripper. Mobil has developed a proprietary baffle design that has been demonstrated to extend the efficient range of an annular stripper. This new baffle design is being offered by Kellogg, and it is commercially being demonstrated in three FCC units. In one case where it was installed, the commercial unit saw a 40F decrease in regenerator temperature and enjoyed the result of increased catalyst circulation rate and conversion. In another case, 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.
Effect of Mass Flux on Stripper Efficiency
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QUESTION 26. 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 2.5 fps, the bed becomes turbulent and the term bubbling does not technically apply. However, 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. Cyclones can be made to handle very high catalyst loadings, however the diplegs must be long enough to properly pressure balance and large enough in diameter to handle the flow. Most refiners tend to limit the operation of their regenerators to about 3.5 fps to maintain catalyst retention with losses near original design. In one refinery we are aware of, the regenerator velocity is about 4 fps with catalyst losses roughly twice that expected in a new unit designed for about 2.5 fps. In another unit, 4.25 fps superficial velocity is claimed with no added catalyst losses. For reference, a general rule of thumb I use is 2 1b/hr loss per 1000 bbl/d for a typical high-efficiency, two stage cyclone system in a moderate pressure regenerator operating at about 2.5 fps to 3 fps. (Losses due to fresh catalyst addition must be added to this figure.)
JOHNS:
Valero has implemented advanced controls on the heavy oil cracker, which include pressure balance and regenerator pressure control. There have been no problems with the expander caused by implementation of these controls. System problems that have been encountered relate to interactions between the various pressure controllers on the combustion air blower, regenerator, and expander. One should examine interactions specific to ones unit when implementing advanced controls.
KELLER:
Practical cyclone loadings of 2.5 fps to 3 fps are a good design range. Lower velocities will shift the CO combustion and heat to the regenerator bed and away from the cyclones and will reduce afterburn. This requires less steam in the cyclone area and generally will provide smoother regenerator burn operations.
QUESTION 27. 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. However, our multivariable advanced controller does not directly control the expander. Our expander inlet and bypass control valves are controlled by the reactor/regenerator differential pressure (hard-wired) controller. Its set point can be changed by a single output (software) controller to minimize the expander bypass control valve opening. The hard-wired controller is allowed to range from +5 psi to -5 psi reactor-regenerator differential pressure; the advanced controller is restricted to +2 psi to 0 psi reactor-regenerator differential pressure. The regenerated catalyst slide valve differential pressure is also programmed to restrict the advanced controller during unusual conditions; but it is not the controlling signal during normal operation. Our multivariable advanced FCC controller directly sets the suction pressure to the wet gas compressor, which indirectly determines the reactor, regenerator, and expander pressure.
QUESTION 28. 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. There are several points that should be considered. First, the power recovery economics should be included in theoptimization software. Second, if you have constraints on downstream equipment from the expander, particularly temperature constraints, they also need to be considered in the optimization software. We have installed and are operating our advanced control/optimization controls on our Corpus Chrisri, Texas refinery catalytic cracker without problems in the expander section.
We are aware of an extensive distillation method that is described in Standard Methods of Water and Waste Water Analysis. It gives very good results. It will give you total cyanide by proper treating of the sample, or an existing cyanide by running the sample as is. However, it is a very tedious test. The results obtained are very accurate, 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. We prefer to use what is called a spot or Prussian blue test. It is a much simpler test to run and easy for operators to do. All one has to do is take a piece of filter paper, pour some overhead water on it, and put a couple drops of ferric chloride onto the filter paper. If the filter paper turns blue, there is a ferrocyanide complex. This shows that the
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cyanide is reacting with the metal in the overhead and is a clear indication that a better corrosion-control program is needed. As I said, this is a very quick and easy test for the operators. So, you can generate more data and have a much better understanding of what is going on in the unit.
KELLER:
for a pressure increase. It just seems to be much more practical.

QUESTION 29. What markets exist for FCC slurry oil, and what are typical specifications? ABRAHAMS:
EPA method 335 is a reliable method used by Ultramar and most regulatory agencies. We charge only hydrotreated feed (less than 3000 ppm Total N) to our FCC unit. Our free cyanides vary from 1 wppm to 4 wppm in the washwater effluent at 2 gpm per MB/D of FCC feed. We have seen hydrogen activity jump above 3 psi per day from our probes when the free cyanides jump above 10 wppm. 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. However, no other vessels showed any damage. The ASTM grade 516 - 70 carbon steel plate used in our original primary absorber exceeded the specification for inclusions caused by impurities.
ROSS:
We have been in two markets for FCC slurry oil. One market is heavy cutter for fuel oil, and typical specifications are: viscosity 250 centistoke, sulfur 6.0 wt%, flash 140F, BS&W 1%, ash 0.1 wt%, pour 60F, vanadium 300 ppm, aluminum 200 ppm, and SFH 0.15. Another market is carbon black feedstock. Typical specifications are: API of 0, sulfur 3%, viscosity @ 210F of 80, flash 150F, ash 0.05%, BS&W 0.5%, pour 60F, potassium 2 ppm, sodium 10 ppm, BMCI 126, pentane insolubles 20%, and asphaltenes 6%. The consensus in the earlier panelists discussions was that whatever you have, if you can get into the market, the specifications can be different.
ROSS:
The ASTM methods for measuring cyanides in waste water are D2036 and D4282. Absolute control of the cyanide level is difficult without frequent analyses, however some operators have noted a simple color check of the washwater where a yellowish tint indicates adequate polysulfide additive to control corrosion, and a bluish tint indicates ferrocyanides and trouble. Although the actual levels of cyanide that cause problems are unclear, many control to about 20 ppm to 30 ppm in the washwater.
How the water sample is collected is also important in obtaining accurate cyanide results. The sample should be collected to ensure no air is allowed into the sample bottle.
Mr. Keller mentioned something about hydrogen probes. We put hydrogen probes on our FCCU in Wilmington, California in 1992. We have yet to see any pressure buildup in them. I am not satisfied with the way they are put together. They consist of a pad that is welded on the vessel. Then a top assembly that consists of the pressure gauge and a thermometer that snaps on through an O-ring. I think that if the hydrogen were tenacious enough to get through a steel shell, it could probably pass that O-ring as well. Since then, a Canadian company has come up with a design called Beta Foil that looks much better to me. It has several salient features that I like. It covers several square feet. It has a vacuum-type attachment, 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. 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. The feedstock must be very aromatic and the cracker operation carefully controlled with a bottoms cracking catalyst to produce this material. Filtration may be required to meet solids content specifications. Increasingly tighter specifications are placed on fuel oils and now alumina content must be controlled to avoid engine fouling. A limitation of 200 ppm alumina typically sets the maximum catalyst content at about 1000 ppm. Power stations can accept higher levels with a typical sulfur specification of 2%. Carbon black and needle coke are attractive markets if the stringent product specifications of density, viscosity, and boiling range can be met. For carbon black a 500 ppm ash limit and 2% S limit are imposed. Other outlets include asphalt or coker feed.
KELLER:
Almost all West Coast FCC slurry oil goes into the carbon black market or 0.5% sulfur Fuel Oil market which is exported to China or Korea. A small amount is sold into the domestic industrial market. Typical specifications range as follows:
Gravity, AP1 Visc, cst @ 122F Sulfur, wt % less than 1 to 8 80 to 180 0.2 to 1.1
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SOLIS:
We feed our slurry to our coker to prevent it from making shot coke. I have co caution, however, and this has been in NPRA QSLA transcripts before, to make sure not to set up a refractory recycle if coker gas oils are charged to the FCCU. We counsel about this, but the coker supervisors keep forgetting, and we have to keep reminding them to keep their coke drum temperature up. As I understand it, the lower the slurry API the better it is for the coker. The API of our slurry is typically around zero.
QUESTION 30. When processing solvent deasphalted oil in an FCCU, 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. We have observed that the catalytic cracking selectivities may correlate with the DAO carbon content. When this value is relatively low (MCRT=1.7 wt%), the conversion, gasoline, and LPG yields are higher than that for a typical VGO. The higher paraffin content in the DAO (versus VGO) explains these results. However, if the DAO has a large carbon content (MCRT=2.8 wt%), conversion, gasoline, and gas yields are lower for the same coke production. The following data are provided as an example of the previous statements.
VGO Aniline point, C Density, Kg/m @ 15C MCRT, wt % Viscosity, cst @ 100C MAT Activity, % Gasoline Yield, % Total Gas Yield, % LPG Yield, % Coke Yield, %
3
DAO-1 114.8 912.5 1.70 46.1 74 48.5 21.0 18.8 4.5
DAO-2 112.4 921.3 2.80 59.4 63 43.5 15.0 13.6 4.5
92.4 905.9 0.24 8.93 66 44.5 17.0 15.7 4.5
The most important parameter is Conradson carbon residue (CCR). 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 50F. The second parameter is aromatic carbon CA content, measured by the n-d-M method. An ~ 1 wt% change in CA affects conversion by ~ 2 vol% and regenerator temperature by -20F. The next important parameter is nitrogen, especially basic nitrogen, due to the immediate effect on conversion and yield selectivities. Approximately 500 ppm nitrogen affects conversion by -3.75 vol% and regenerator temperature by ~ 10F. The final parameter is contaminant metals, especially Ni and V. A change of ~ 330 ppm equivalent Ni (Ni + 0.25V) affects conversion by ~ 1 vol% and regenerator temperature by ~ 20F. A refiner might also want to look at sulfur levels, due to environmental constraints, in the flue gas and products.
ROSS:
H. DAVID SLOAN (The M. W. Kellogg Technology Company):
As with the previous question on deasphalted oil (DAO) quality monitoring, the quality of DAO is really on a sliding scale between VGO and VR, depending on the depth of deasphalting. 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. In general, however, the DAOs we have encountered have conversion precursors or gasoline precursors 30% to 50% lower than VGO of the same source. The poly-aromatics are generally higher, resulting in more catalytic coke for a given conversion level, and the contaminant coke is also a factor. The feed-derived coke due co contaminants as measured by Conradson carbon tests may well be less than equivalent asphaltene rich resids; however, precise commercial measurements are difficult as the amount of DAO in the feed blend is typically less than 20%.
This quest-ion is supplementary to Question 11 from the General Processing Session. I must admit when I first saw the question, 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. Given that there is very little in the literature on the subject and specific results of our work are not yet ready for publication, I can only offer the following remarks. We heard several rules of thumb this morning on the effect of FCC properties on conversion. Reports from our ROSE licensees indicate that as an incremental FCC feed, 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. For example, a four Conradson carbon deasphalted oil will make coke more like a two Conradson carbon heavy gas oil. Other yields should follow correlations for heavy gas oils since the deasphalted oil is a product of physical separation and not a cracked material.
RICHARD STREET (Criterion Catalyst Company):
We see a trend in refiners charging heavier fractions, including deasphalted oil (DAO), to FCC feed hydrotreating units. We have designed catalyst systems chat are in FCC feed hydrotreating units which process as much as 40% deasphalted oil. These catalyst systems provide a much higher stability in overall activity than a conventional
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FCC feed hydrotreating catalyst system processing deasphalted oil. 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.
QUESTI0N 31. 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 (190C) LCO DO Coke 1.0 wt % -2.7 -4.4 +4.3 +1.6 +0.2
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. (All of the usual conditional statements regarding crude type and processing severity apply.)
DEADY:
In general, the visbreaker gas oils are fairly aromatic and refractory, and tend to make more coke and gas than conventional FCC VGO feeds, i.e., a lot like coker gas oil. I have data from a couple of MAT studies comparing VG0 feed and visbreaker feed by themselves, and then another study that compares the VGO feed with 5% and 10% blends of the visbreaker feed.
QUESTION 32. What is the industry experience when processing used tube oil in the FCCU? What pretreatment is recommended for this stream? DEADY:
the ECAT, causing additional coke and gas. Finally, lube stocks can be either very paraffinic or very aromatic. Obviously, if there is a choice, you would rather process the paraffinic ones. But I found that most refiners do not have a choice. In fact, 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. When processing lube oils, FCC operators generally see a dramatic decrease in their ECAT activity and unit conversion, and that is probably their first clue that something is going on. When we look at our ECAT database, we typically see an increase in calcium and/or zinc that tracks identically with the loss in conversion. The loss of conversion ranges from about 0.2 of a microactivity number to 0.6 of a microactivity number for every 100 ppm of calcium oxide increase. And for zinc we see a range anywhere from 0.9 of a microactivity number to about 2 microactivity numbers for every 100 ppm of zinc oxide. These levels are directly associated with lube oils. The highest calcium numbers that we have seen are about 6000 ppm. The highest zinc numbers that we have seen are about 3300 ppm, indicating significant amounts of lube oil being processed. Finally, we observed something this year that was interesting. It appears that one mechanism by which used lube oil deactivates catalysts is by pore plugging and shutting off the active sites. 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. However, the surface area that is measured by nitrogen method was unaffected. We thought that was interesting and took a closer look. When we measured the pore volume with mercury, which looks in more detail at the larger pores, 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, indicating plugging of the larger pores.
SHEN:
To answer the first part of this question on industry experience when processing used lube oil in the FCC, we have actually observed a number of refiners in the past year that have operated this way. Generally, lube oil stocks contain fairly high amounts of FCC catalyst contaminants. Examples of this are sodium, magnesium, potassium, and vanadium. All those tend to deactivate the cracking catalyst. Additional contaminants (for example, copper, zinc, manganese, and vanadium) will produce higher coke and gas. In addition, the additive solvent package can contain halogenated hydrocarbons, 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. The high paraffinic molecules crack easily. However, because the amount of lube oil fed into the FCCU was relatively small, the data did not show a noticeable impact on gasoline octane and olefin yield. In general, used lube oils tend to contain plenty of alkali metals (calcium, magnesium, zinc, etc.), and these metals can rapidly deactivate FCC catalyst if any significant volume is processed. A typical approach people use is to process this stream through a rerun fractionation tower (or vacuum tower). The metals, as a general rule, will have the tendency to stick with higher boiling range molecules. The distillate from the rerun tower can either feed to the FCC directly, or, if you have spare capacity in
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the FCC feed hydrotreater, you can send it there to remove these metals. The fractionation bottoms can be sent to the coker.
SOLIS:
We have never directly processed used lube oil in our units. But, upon request from the Madrid Environmental Authorities, we have made a trial with a distillate cut (350C to 550C) from a used oil collecting factory. 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, we observed the following differences:
VGO Conversion, % Total Gas, % Gasoline, % LCO, % HCO, % Coke 62 43 14 26 17 5 350C to 550C Used Oil Cut 81 58 20 15 7 3
DELBERT F. TOLEN (Rocky Mountain Salvage & Equipment):
If you would like to come out, ninety miles west of me is the smallest commercial FCCU in the world, 500 bbl/d, and it runs on nothing but used lube oils.
Environmental Control
QUESTION 33. 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 . The varying influence of fresh catalyst additions and normal catalyst attrition make reliance on this type of system for very low discharge levels risky. When present or future flue gas treatment for SOx and/or NOx is required, a wet scrubber system similar to the Belco or Exxon scrubber can be used. Due to the requirement to provide efficient contact between a fine mist of water and flue gas, catalyst capture automatically results. Effluent concentrations of 50 mg/Nm3 or less are common. When very strict regulations are in force, an electrostatic precipitator is the clear choice. Effluent levels as low as 10 mg/Nm3 have been achieved at a price with typical levels well below 50 mg/Nm3. Other systems, such as sintered metal or ceramic filters, are still in the proving stages but potentially offer extremely low effluent levels. Another consideration when looking at particulate control is the level and control of condensibles which are typically included in particulate tests. The SO3 in the flue gas stack is a prime example. 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, which for some refiners, has been the difference between compliance and non-compliance in the past. As a word of caution, when the environmental limits are below about 200 mg/Nm3, cyclones in the regenerator will not meet this specification by themselves. The design of these cyclones should not be pushed in an attempt to meet the limits; rather the appropriate downstream units should be designed to handle normal regenerator emissions. Do not jeopardize the regenerator cyclone design by pushing the design limits in a futile attempt to meet emission limits.
The types of commercially proven particulate removal technology available fall into three categories cyclonic, wet scrubbing, and electrostatic capture. Cyclonic separation systems, 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, can achieve particulate emissions reduction to about 75 mg to 150 mg/Nm3 on a consistent basis. The newer third stage cyclones with many small cyclones fitted inside a vessel claim efficiencies approaching 50 mg/Nm3 in the discharge. However, Stone &Webster would be reluctant 80 Heavy Oil Processing
ABRAHAMS:
At one of our plants, we had one of those million dollar Oh-shoot projects. 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. The device was successful in removing mass from the stack up to about a ton and a half per day, 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.
HANSEN:
Valero installed a Belco EDV Scrubber on the HOC unit flue gas in October 1994. The scrubber easily makes the permit maximum allowable particulate level of 0.57 lb of particulates per 1000 lb coke burned. The EDV scrubber filtering modules employ condensation of water vapor onto submicron particles to increase their mass. The enlarged particles and mist droplets are removed from the flue gas by mechanical impaction created by the filtering spray nozzles. The scrubber was instrumental in allowing Valero to be the first petroleum refiner to win the Texas Governors Award for Environmental Excellence in 1995. Electra filtering modules can be used if significantly lower emission levels are required. These are similar to filtering modules but have a rigid pipe electrode axially mounted inside each module. The ionizing effect of the electrode gives the wetted particles and mist droplets a negative electrical charge. 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, mechanical impaction and electrostatic attraction. Power usage by the electrodes is very low since the current levels are on the order of 10 milliamps. Electra filtering modules have been used extensively on incineration and SO3 applications.
KELLER:
Our FCCU was built in 1982 with an electrostatic precipitator. We lose 50 tons of catalyst a month. Three go out the stack, 40 are precipitated, and 7 are in the slurry oil. Our recent stack tests have measured 24 mg to 34 mg of total particulate matter per dry standard cubic meter.
MANFRED OEHNE (Polutrol Europe):
I would like to submit a statement in favor of the modern, dry/cyclonic rype third stage collectors. There seems to be just no alternative to a modern third stage collector whenever a power recovery installation operates downstream of the FCC generator. But even to check emission levels for purely environmental reasons, this collector type is a wise choice.
Cyclonic third stage separators have come a long way. Over the years their design, overall functionality, and catalyst collection capabilities have been improved dramatically. Nowadays, to arrive at emission levels of 70 mg/Nm3 to 80 mg/Nm3 (dry) is absolutely no problem. 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. And this impressive performance can be achieved without any underflow system and/or fourth stage collector required. A series of recent tests performed at two European refineries involving our modern dry type third stage collector, EURIPOS series, has produced clear evidence that fractional particle efficiencies on the order of dsm(5e) = 0.8 to 1.2 micron can be achieved without a hitch. Such performance is very much in the range of scrubbers and ESPs. The basis of such impressive performance, of course, is not an outdated seat-of-the-pants design approach, but instead relies upon modern, up-to-date, and highly advanced mathematical modeling processes. Where do we go from here-what does the future hold in store? With great certainty, the mathematical modeling will be steadily improved, allowing even better designs via fine tuning of the rather complex processes taking place inside a cyclone. Testing of operating systems in the field, i.e., allowing an actual check of the mathematical models, is a requirement that should be pursued with diligence by everybody involved. For example, the apparent nonlinear behavior of particle densities in a force field needs to be explored further. This undoubtedly will require a closer cooperation between the catalyst manufacturer, the refiner, the engineering companies and, last but not least, the designer of dry type cyclonic third stage collectors. On a final note, referring to a previous question (Question 21), 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, but their overall efficiency normally would be in the 40% to 50% range. He furthermore claimed that based upon an identical particle input analysis, 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%. Although his statement may have been made in a purely self-serving manner, it nevertheless leaves the impression that a few large diameter cyclones, under the premises of identical operational constraints applied, 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). His statement, of course, is wrong, unproven, and unscientific.
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Contrary to what was claimed, I want it to be known that it is really the other way around.
ROBERT L. BROWN (Pall Process Filtration Company):
testing, laser inspections). What results were obtained and what were the approximate costs? FRONDORF:
Pall blowback filtration systems remove more than 99.9% of the solids in the flue gas. At this efficiency, emission standards of 6 mg per normal cubic meter can be met without additional separation equipment.
B. Residual Oil Upgrading-Delayed Coking

Mechanical
QUESTION 34. Has anyone automated a Wilson-Snyder type switch valve for totally remote operation? It so, how was the lowering and raising of the collar accomplished? JOHNS:
We have not had any experience with the Wilson-Snyder type valve.
KELLER:
We have purchased, but not installed, an electro-hydraulic actuator from Wilson-Snyder. The new actuator should reduce operator exposure to the existing WilsonSnyder coke switching valve. The new actuator uses hydraulic pistons to hammer seat and unseat the plug of this highly mechanical valve, as well as rotate the plug ports for flow direction changes. This type of hydraulic actuation replaces the upper jackscrew collar of the valve, which is normally used to raise and lower the plug assembly. 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). The PLC will control the time-sequenced piston operation either locally or from our remote DCS. To ensure proper drum isolation during coke cutting, an operator will still manually close an isolation valve between the Wilson-Snyder switching valve and the full drum.
FRONDORF:
CITGO has used acoustic emission (AE) testing for locating cracks in coke 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. We will follow up with UT and visual testing of the suspected points. We have had a high rate of success locating cracks before they become leaks. We have also utilized high temperature strain gages to monitor coke drum stresses during the coke cycles, particularly in the areas of recurring cracking and bulging. This has aided in predicting when cracks and bulges are beginning to develop. We also use these data for finite element analysis when designing new drums. We have utilized automated laser bulge mapping to size and track the growth of bulges in the coke drums. This technique has proven to be a very useful tool in evaluating the condition of drums, particularly older drums, and comparing that over time. The mapping is performed utilizing the existing drill stem rigging. It is done immediately after coke drum cutting is complete. Normally it can fit into your cycle on a reasonable drum cycle time, so there is not a lot of disruption to normal operations. We have been very satisfied with all three techniques. The costs are fairly high, so we do not use them on a regular basis; rather, we use them periodically on a planned basis, either during the year or before a scheduled turnaround. There is one other method that our Corpus Christi refinery utilizes, but I am not very familiar with it. It is named U Plus and uses an ultrasonic imaging technique for crack detection. It may replace acoustic emissions in the future and they say it is considerably less expensive.
KELLER:
We are aware that Wilson-Snyder has developed a system to fully automate their switch valve. We do not have direct experience with one, to date. The use of ball valves in this service is becoming more common, and this type application has also been fully automated. We are preparing to buy two such valves for one of our Lake Charles cokers.
QUESTION 35. Please discuss new technologies to monitor coke drum bulging and cracking, (e.g., acoustic emission
In January 1995 CIA was contracted to conduct a laser evaluation and videotaping of our four 24-ft ID coke drums. These four clad-lined coke drums have been in service 14 and 25 years. The laser evaluation cost $80,000 and indicated no bulging. In 1993 a WFMT examination of the coke drum ODs identified a crack in a girth weld of one of the drums. The laser evaluation conducted in 1995 did not identify bulging associated with this crack.
ABRAHAMS:
We can confirm the approximate price. We used Custom Industrial Automation of Canada to inspect our four coke drums. We found no bulges, 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.
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KEITH OSBORN (Farmland Industries, Inc.):
I would like to poll the panel and the floor. Have you ever experienced, or are you aware of, 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. We have not noticed anything due to biological causes. I think it would be possible to shock the system if it is truly a biological problem.
QUESTION 38. Describe your experience with mechanically decoking (pigging) coker heaters, specifically in the following areas: a) impact on tube life from metal loss; b) downtime required as compared to steam/air decoking; c) impact on heater run length; d) success at removing coke formed as a result of high sodium in the feed as compared to steam/air decoking. JOHNS:
We have not heard of anything catastrophic.

MORGAN:
We have two cokers, and I am not aware of any failures of that nature.
FRONDORF:
All the failures that I am familiar with have been in the cracking mode.
QUESTION 36. 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 believe we do not have justification for the metallurgy yet, 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:
Neither of our facilities has 9Cr V tubes. Both facilities have nine-chrome.
QUESTION 37. 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. We have not found a cost-effective way to treat it. Chemical treatment is a very expensive option. What solutions have been successful? SHEN:
We use slides of a thermographic scan of the large lines coming out of the coker drum, which show, from a thermal color gradient, a coke ball near the top. This is how we detected plugging and high pressure drop in this line. The intensity of color gives you the degree of temperature. With regards to the exact question on pigging, one plant has successfully mechanically pigged the lines. We had observed that usually all laydown material had been cleaned by this pigging until this last time in July. For some reason, after pigging, we now have a short cycle on this particular heater for the first time. Perhaps something went wrong in the procedure. We are usually quite successful. One needs to consider that heater design may have a lot to do with the ease and even the feasibility of pigging most heaters.
VAN IDERSTINE:
My answer to this question could be off the mark, so I will keep it short. We have not seen a cutting water system corrosion problem caused by microbiological factors. What we have seen is that most problems are erosion rather than corrosion. We believe that erosion is caused by coke particles. 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.
JOHNS:
We do not do any mechanical pigging of our coker unit heater. We do a steam/air decoke. On the vacuum unit heater, we used mechanical pigging once, but really did not find very much coke, so we have not done any decoking of that heater in the last three years. 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. 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. Furthermore, we are consistently producing anode grade green coke.
GARY HUGHES (Conoco Inc.):
At one of our plants, 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. To date, we have not experienced any significant metal loss due to the pigging. The stream-to-stream downtime required for pigging a furnace is typically 2 to 2 days. Due to the relatively high cost of pigging, we have been reevaluating the steam/air
83
decoking technique. And since doing so, we have been able to improve our steam/air decoking procedure, allowing us to reduce the stream-to-stream time from 4 days to 3 days. Concerning heater run lengths between decoking, we see similar run lengths between furnace decoking when utilizing the pigging technique versus steam/air decoking. Therefore, 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, we have found that the pigging technique does a much better job of removing nonorganic deposits, which sometimes build up in the return bins of the furnace tubes.
maintaining a total cool-down time, which we have done as we have shortened cycle times over the years. We have not seen a coke quality change when we have eliminated this step.
QUESTION 40. What are refiners doing with their coker naphtha besides sending it to reformers and FCC units? VAN IDERSTINE:
Process
QUESTION 39. During the coke drum cooling/cutting part of the coking cycle, immediately after switching to blowdown, steam is injected into the bottom of the full drum (called big steam") for one-half to one hour. After the big steam step, water is injected into the bottom of the drum. Has anyone eliminated the big steam step in order to reduce cycle time? If so, have changes in coke quality or drum integrity been observed? SHEN:
We split our naphtha in the coker. We take a 350F end point on our light naphtha and we send that over to our heavy naphtha unifiner. The heavier coker naphtha goes to our distillate hydrotreater. The obvious negative aspect of feeding coker naphtha to any hydrotreater is silicon poisoning from silicon in the antifoam.
JOHNS:
We have, at certain economic times, charged some of the light coker naphtha material to our hydrocracker and that has usually been in the range of a 360F to 370F end point. This has been done when we were either short of HCU feed or long on reformer charge. You need to watch the heat transfer on the preheat exchangers, of course, and an inhibitor/disbursement material will be required for this light coker.
QUESTION 41. 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. We have seen several refiners skip the big steam step to shorten cycle time. As for the question of coke quality and drum integrity, we are concerned more about drum integrity than coke quality. After the small steam cycle, the coke bed and the drum are still at very high temperatures. Any water injection would convert to steam. People adjust the water rate by watching how fast the pressure rises, but there is always the potential of over-pressuring the drum. The other concern we have is that when you add water to a hot coke drum, the water does not distribute as well as the steam, and the coke in the drum is not always in a homogeneous form. There is a possibility that channels in the coke bed exist. If a channel is directed toward the vessel wall, cold water can hit the hot metal wall. The resulting localized thermal stresses could potentially cause vessel cracking. As for coke quality, feedback indicates that refiners cannot tell any difference.
FRONDORF:
Our cokers are designed to drain the quench water through a line teed into the bottom head gooseneck. The water goes directly into the sluiceway and is recovered in the dewatering/clarifier system. Occasionally we get a plugged drum or drain line. To drain the drum in this case, we follow a written procedure. It requires that a two-man team wearing proximity suits remove a continuous quarter to half section of the bottom head bolts. They start with the bottom head bolts furthest away from the catwalk and work their way back to the platform. Rarely do more than half the bottom head bolts need to be removed to establish an adequate drain.
SHEN:
The Lake Charles, Louisiana refinery still has a big steam step, but it is considerably shorter than the half hour to one hour mentioned in the question. It is more on the order of 5 to 10 minutes. At the Corpus Christi plant, we begin the quench cycle immediately after switching to blowdown, i.e., the big steam step has been eliminated. 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. We believe it could be a hazardous operation. 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. If the operator is having difficulty draining the drum because of blockage, or for any other reason, we would
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, or simply making the drain line larger. If the drain line restriction problem (blockage) happens frequently, it may be because of shot coke production.
VAN IDERSTINE:
QUESTION 43. What has been the experience processing used lube oil in coker units? What pretreatment is done, if any, 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. The only time you get into that situation is if your bottom drain becomes plugged for some reason. If you ever open the bottom head flange without proper draining, three steps are recommended. First, ensure that the drum has been adequately cooled. Second, ensure that the bottom head can be held in place while the flange bolts are removed. Most drums are equipped with some type of hydraulic or pneumatic lift for raising and lowering the bottom head. Personnel involved in this step should wear protective equipment when unbolting the head. Last, but not least, evacuate the area below the drum prior to lowering the head. Try to run your delayed cokers in a manner that will avoid the potential of plugging your bottom drain.
FRONDORF:
At one of our plants, 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, just upstream of the preheat furnace. We have had essentially no pretreatment. We made sure that the oil did not contain any free water after transfer to an existing fuel oil tank. We estimated the benefits to be that the oil, in addition to providing recycled benefits, would break down to a yield of 4% butane, 3% pentane, 8% naphtha, 82% gas oil, and 3% coke. No corrosion problems have been associated with this procedure.
ABRAHAMS:
I agree with the others. We do not regularly drain the drum by dropping the bottom head. Where that would become necessary, we have a written procedure that follows the same guidelines that were previously mentioned. At our Corpus Christi, Texas refinery, we have an automatic remote-operated unheading device that gives us more flexibility when this problem occurs. We are currently on 13-hour cycles and are considering going to 12-hour cycles. 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, which would automatically swing out; how to control the spilling of the hot water and loose coke on the deck; barricades; etc.
QUESTION 42. Is anyone pressure draining coker drums using nitrogen, and if so, what has been the impact on drain time? SHEN:
We do not have experience on a delayed coker, but we do on our fluid coker. We have been collecting used lube oil from local company service stations and also from Delaware. We have not had any corrosion problems or any other operating problems as a result of this. Most of the benefit has been in public relations from working with the local authorities.
FRONDORF:
Our LYONDELL-CITGO joint venture had been processing used lube oil as vapor quench to the coke drum overhead vapor line. No pretreatment was performed on this oil. No corrosion problems were noted in the coker itself. However, the downstream hydrotreater that processes the coker naphtha experienced corrosion from the outlet of the reactors through the cold flash drum circuit. One line failure was experienced. The cause of this corrosion was apparently organic chlorides contained in the used lube oil fractionated into the coker naphtha stream. Chloride levels as high as 40 ppm were noted in the naphtha. We have since discontinued processing the used lube oil.
We do not know of any refinery pressure draining the coke drum using nitrogen or steam. If something must be used, steam would be a lower cost selection over nitrogen. At least you can recover the water. One potential problem with pressure draining is that too high a pressure difference across the coke bed could collapse your coke bed, resulting in a blockage problem in the lower section of the coke drum. 1995 NPRA Q&A Session on Refining and Petrochemical Technology 85

1995 NPRA Q&amp;A - Heavy Oil Processing

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1995 NPRA Q&amp;A - Heavy Oil Processing

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HEAVY OIL PROCESSING

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

EDWIN D. TENNEY (GE Environmental Services):

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

GEORGE A. SMITH (Exxon Research & Engineering Company):

Heavy Oil Processing

NOx from Commercial Regenerators

1995 NPRA Q&A Session on Refining and Petrochemical Technology

decreased afterburn to 5C and achieved a NOx reduction of 30%.

Heavy Oil Processing

Kellogg Comparison Of Pollution Control Options

G. ANDREW SMITH (INTERCAT Inc.):

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

TUAN NGUYEN (The M. W. Kellogg Company):

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

PAUL FEARNSIDE (Nalco/Exxon Energy Chemical Company):

1995 NPRA Q&A Session on Refining and Petrochemical Technology

JAMES D. WEITH (Unocal Corporation):

Heavy Oil Processing

Effect of Mass Flux on Stripper Efficiency

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

for a pressure increase. It just seems to be much more practical.

1995 NPRA Q&A Session on Refining and Petrochemical Technology

JAMES D. WEITH (Unocal Corporation):

DAO-1 114.8 912.5 1.70 46.1 74 48.5 21.0 18.8 4.5

DAO-2 112.4 921.3 2.80 59.4 63 43.5 15.0 13.6 4.5

92.4 905.9 0.24 8.93 66 44.5 17.0 15.7 4.5

H. DAVID SLOAN (The M. W. Kellogg Technology Company):

Heavy Oil Processing

1995 NPRA Q&A Session on Refining and Petrochemical Technology

DELBERT F. TOLEN (Rocky Mountain Salvage & Equipment):

1995 NPRA Q&A Session on Refining and Petrochemical Technology

B. Residual Oil Upgrading-Delayed Coking

Heavy Oil Processing

KEITH OSBORN (Farmland Industries, Inc.):

We have not heard of anything catastrophic.

1995 NPRA Q&A Session on Refining and Petrochemical Technology

Heavy Oil Processing

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1995 NPRA Q&A - Heavy Oil Processing

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