Refining Technologies

Catalagram Technical News

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A Message from the Editor

Grace Davison has always been known for its outstanding FCC technical service. Over the last year, we have raised the standard by further increasing our technical staff and services. Catalagram Technical News is a new publication from Grace Davison and part of our increased FCC technical service initiative. The goal of this publication is to provide the reader with solutions to common FCC problems. Published on a quarterly basis, Catalagram Technical News brings short articles describing FCC troubleshooting events, rules of thumb and other technical information. In this issue, we explore why sample analysis is a key part of FCC troubleshooting. Jeff Koebel describes which catalyst samples are critical and the importance of historical data. Adam Kasle describes a recent event where a refiners FCC unit experienced a sudden increase in catalyst losses. Evaluation of catalyst samples described in Jeffs article proved key to understanding the source of the catalyst losses. I hope this article provides you with useful technical information and insight. After reading this quarters issue of Catalagram Technical News, I encourage you to save it for future reference. Your comments on how to improve this publication are welcome and encouraged.

David Hunt FCC Technical Service Manager david.hunt@grace.com

HISTORICAL DATA ARE KEY TO TROUBLESHOOTING CATALYST LOSSES

By Jeff Koebel FCC Technical Sales Manager Grace Davison Refining Technologies Chicago, Illinois roubleshooting catalyst losses from an FCC can be a complicated process. Having the proper data is an essential part of any successful troubleshooting effort. An historical benchmark for the units normal catalyst losses makes identifying potential causes for elevated catalyst losses easier. Grace Davison Refining Technologies can assist with this effort by routinely analyzing main column bottoms

for solids content, particle size distribution and particulate chemical analysis. If your FCC is equipped with an ESP or a wet gas scrubber, Grace Davison can analyze the material collected for particle size distribution and chemical analysis. These samples should be collected once per month to establish a baseline. During this time when the baseline is being developed, Grace Davison recommends establishing a good catalyst balance around the unit over the course of several months. Keep track of catalyst additions and withdrawals as well as losses to the flue gas system and the main column bottoms. (continued on page 2)

W.R. GRACE & CO.-CONN. > 7500 GRACE DRIVE > COLUMBIA, MD 21044 > TEL (410) 531-4000 > FAX (410) 531-8253 > catalysts@grace.com

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(continued from page 1) Generally, the refinery lab analysis for the main column bottoms streams gravity and solids content, combined with the net bottoms rate, can readily establish the rate of catalyst loss to the main column. If your FCC has a wet gas scrubber, the purge water rate and the refinery lab analysis of the purge water solids content is all that is needed to know the regenerator side catalyst losses. If an ESP is present, good documentation of the amount of catalyst removed from the ESP hoppers is necessary. While there will typically be some scatter in these data, over time you will be able to confidently establish a baseline rate of catalyst losses for your unit during periods of normal operation. This catalyst balance can be used as a cross check of the analysis of main column bottoms and scrubber purge water for solids content, as these samples are sometimes subject to considerable variation. As a rule of thumb, a well-contained FCCU should have catalyst losses less than 0.10 pound per barrel of feed. Armed with this information, refinery staff can track the rate of catalyst losses and the particle size distribution (PSD) of the losses to monitor for developing trouble as cyclones approach an endof-run condition. Also, if any unusual catalyst losses occur during unit operation, a sample of the lost material that is analyzed for particle size distribution and compared to the baseline can help establish if the losses were the result of catalyst attrition or some other issue. If enough of the material is present, chemical analysis can establish if the material is catalyst or potentially some additive that is preferentially being lost from the unit. These types of analysis are also not limited to losses that occur during operation of the unit. If the unit experiences unexpected losses during startup or shutdown, these same samples can characterize the catalyst loss and can help to focus troubleshooting efforts on a narrower list of possible causes. Please contact your Grace Davison technical sales manager for further information.

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How will you establish a baseline rate of catalyst losses for your unit?

IDENTIFYING CATALYST LOSS SOURCES: A PROCESS OF By Adam Kasle

FCC Technical Sales Manager Grace Davison Refining Technologies New Orleans, Louisiana ften, identification of the root cause for catalyst losses from an FCC unit is a process of elimination of all the suspected potential causes. This is in part due to the dynamic nature of the FCC process, but it is also due to the fact that there are often numerous potential causes for catalyst losses that will result in the same type of unit behavior. In a catalyst loss investigation, all of the available data must be analyzed and considered in order to rule out possible causes based on the unit symptoms or include them for further investigation.

ELIMINATION

Background
In a recent case, a UOP High Efficiency FCCU undergoing a catalyst reformulation, but operating at otherwise stable conditions, experienced a threeday period in which elevated catalyst losses were observed from both the reactor and regenerator. During this period, the BS&W of the slurry oil increased from the typical level of 0.3 - 0.4 vol.% to 3.0 vol.%. In addition, the hoppers of the ESP, which normally fill in two to three weeks, filled in less than three days. Furthermore, increases in the unit slide valve pressure drops were also observed during the same period. (continued on next page)

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Analysis
The change in the slide valve pressure drops was an indication of improved fluidization properties of the catalyst inventory, which can result from increased catalyst fines in the unit. This was illustrated by the equilibrium catalyst analysis, completed after the losses stopped, which showed the 0-20 micron fraction of the inventory had increased from ~1 wt.% up to 5 wt.%. The increase in catalyst fines in the unit inventory, coupled with the losses from both the reactor and regenerator, led to the elimination of a mechanical issue, such as poor cyclone operation, as a possible cause for the losses and pointed to a source of catalyst fines. In order to identify the source of catalyst fines in the unit, the actions listed below were taken. While an analysis of the slurry ash would normally have been included in this list, no sample retains were available from the loss period to use for the investigation. 1. All metered flows were checked to identify any increases in distributor velocities 2. The operations staff was asked about the use of blast steam during the loss period 3. Samples of the material collected from the ESP were submitted for PSD and chemical analysis 4. A fresh catalyst sample was submitted from the hopper for PSD and attrition resistance 5. Retain samples from the fresh catalyst production were re-tested for PSD and attrition resistance that the attrition resistance and fines content were on target and not significantly different than the old catalyst formulation. Even more conclusive than the properties of the fresh catalyst is the comparison between the properties of the material lost, the equilibrium catalyst, and the fresh catalyst. The table below shows that the chemical properties of the material collected from the ESP were consistent with those of the entire catalyst inventory. Had the incoming fresh catalyst caused the catalyst losses, the metals content of the ESP material would have been lower than that of the bulk inventory due to the lower catalyst age of that fraction. Furthermore, with the (continued on page 4)

TROUBLESHOOTING
tools can make all the difference...

...having the right

Review of all steam flows to the unit did not indicate that any distributor velocity had exceeded its normal parameters. Furthermore, no changes in any unmetered blast flows were made during the period in question. The average particle size (APS) of the material collected from the ESP was 20 Ni, ppm microns. Although these factors appeared to suggest a fresh cataV, ppm lyst issue, the tests conducted on Al2O3, wt.% the fresh catalyst (both from the manufacturing plant retains and RE2O3, wt.% from the unit hopper) indicated

ESP FINES 2181 2295 46.2 2.26

EQUILIBRIUM CATALYST 1945 2288 45.4 2.35

FRESH CATALYST ~0 ~0 49.9 1.23

W.R. GRACE & CO.-CONN. > 7500 GRACE DRIVE > COLUMBIA, MD 21044 > TEL (410) 531-4000 > FAX (410) 531-8253 > catalysts@grace.com

(continued from page 3) ongoing catalyst change, the Al203 and rare earth content of the material collected would also have been different from the total equilibrium catalyst inventory. Since no excessive distributor velocities were evident before or during the catalyst loss period and no changes had been made to any blast points, it was concluded that the most likely cause of the catalyst attrition was an upset of the steam system, such as wet steam. Wet steam entering the reactor would result in excessive distributor velocities that would cause catalyst attrition. However, this would not be evident from the steam flow meters. Troubleshooting any catalyst loss issue can be a difficult task, and having the right tools and information can make all of the difference. Grace Davison can provide technical support in addition to fast results from essential laboratory tests such as equilibrium catalyst, fines, slurry ash PSDs and chemical compositions to assist in these efforts.

Conclusion
The data collected from the unit show that the cause for the observed catalyst losses must have been a general attrition source. The fact that the losses were related to a catalyst fines issue and not a mechanical problem is supported by the APS of the material collected from the ESP (20 m), the losses from both the reactor and regenerator, and the shift in equilibrium catalyst fines content. The properties of the material lost show that the entire unit inventory was the source of the catalyst fines, not just the fresh catalyst.

Please contact your Grace Davison technical sales manager for further information.

SAVE THE DATE

Grace Davison Refining Technologies First North American Technical Seminar June 22-24, 2005 Washington, DC More Information to follow @ e-catalysts.com

Refining Technologies
2005, W.R. Grace & Co.-Conn.

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We hope the information given here will be helpful. It is based on our best knowledge and we believe it to be true and accurate. Please read all statements, recommendations or suggestions herein in conjunction with our conditions of sale which apply to all goods supplied by us. We assume no responsibility for the use of these statements, recommendations or suggestions, nor do we assume any responsibility in the event that our goods or any use of such goods infringe any patents.

W.R. GRACE & CO.-CONN. > 7500 GRACE DRIVE > COLUMBIA, MD 21044 > TEL (410) 531-4000 > FAX (410) 531-8253 > catalysts@grace.com