NUMBE R 100 Fal l 2006 - Grace.com...turing “Cat Cracker Material Heat and Balance”became an...

N U M B E R 1 0 0 Fa l l 2 0 0 6

A message from the editor...

Dear Refiner:

You are holding a milestone in the refining industry: the 100th issue of theGrace Davison Catalagram. What started in 1959 as a modest newsletteron the merits of Davison’s fluid cracking catalysts has evolved into an often-referenced, industry-leading technical publication.

In the 48 years since its introduction, the Catalagram has introduced revolu-tionary technology like zeolite catalysts, combustion promoter additives, catalysts for clean fuels,NOx and SOx reduction additives, and tunable reactive matrices. We’ve published numerousarticles on FCC troubleshooting throughout our history and Issue 59, first published in 1980, fea-turing “Cat Cracker Material Heat and Balance” became an instant classic, the most-requested ofall our back issues, and the foundation for Part III of the renowned Grace Davison Guide to FluidCatalytic Cracking. Most recently, as part of our Advanced Refining Technologies joint venturewith Chevron, we have expanded our content to include articles on hydroprocessing.

Grace Davison and Advanced Refining Technologies are committed to the success of our cus-tomers. This is reflected in the three prongs of the our mission:

Discover: Listen to our customers, be open to new ideas, and respond to market dynamics;

Design: Design products and services to create solutions and processes to improve results; and

Deliver: Deliver value to our customers and execute with speed.

The Catalagram is an important tool in accomplishing this mission. This issue is itself an exampleof how we full our mission: the PrISM article describes how we interact with our customers todiscover new ideas and technology; the Neptune article chronicles the design of a new productto meet refiners' needs; and the NPRA Q&A answers are yet another example of how we delivervalue to our customers not only through new products but through our industry-leading techni-cal service.

We welcome your comments.

Sincerely,

Gregory E. PolingPresidentGrace Davison

IN THIS ISSUE

The PrISM Process for Product Development: A Map for Customer-Driven R&D by E. Thomas Habib, Jr., Director, Customer Research Partnerships,Grace Davison Refining TechnologiesGrace uses a “stage and gate” process for new product development called PrISM (ProductInnovation and Strategic Marketing) When we work with our customers to develop newproducts, we use this process to provide expeditious product evaluation and commercial-ization by considering the technical, as well as the business objectives of the refiner.

2

NEPTUNE: New Generation Cracking Catalyst ReducesGasoline Sulfur by Nearly 60%by Lauren A. Blanchard, Marketing Manager,Grace Davison Refining TechnologiesGrace Davison announces breakthrough catalytic technology for sulfur reduction inFCC gasoline: NEPTUNE, a fully flexible catalyst with industry leading sulfur reduc-tion functionality. This article details a commercial trial of NEPTUNE at CitgoPetroleum Corporation's Corpus Christi, Texas USA refinery.

Answers to FCC Questions for the 2006 NPRA Q&A by Dennis Kowalczyk , National Technical Sales Manager,Grace Davison Refining Technologies

8

18

CATALAGRAM 100Fall 2006

Managing Editor:Joanne Deady

Contributors:E. T. Habib

Lauren BlanchardDavid A. Hunt

Dennis KowalczykCharles W. Olsen

Greg RosinskiGeri D’Angelo

Please addressyour comments to

[email protected]

W. R. Grace & Co.-Conn.7500 Grace Drive

Columbia, MD 21044(410) 531-4000

www.e-catalysts.com

©2006 W. R. Grace & Co.-Conn.

Use the Hydrogen in Coke Number to Determine CokeMake Accuracyby David A. Hunt, Technical Service Manager,

Grace Davison Refining TechnologiesThis article proposes refiners use the hydrogen in coke number to help confirm theaccuracy of their coke make, other heat balance parameters and flue gas analysis.

14

The information presented herein isderived from our testing and expe-rience. It is offered, free of charge,for your consideration, investiga-tion and verification. Since operat-ing conditions vary significantly,and since they are not under ourcontrol, we disclaim any and allwarranties on the results whichmight be obtained from the use ofour products. You should make noassumption that all safety or envi-ronmental protection measures areindicated or that other measures may not be required.

Grace Davison/ART - People in the News 16

ApART Catalyst SystemTM Excels in Commercial Service:Update on Advanced Pretreating by ARTby Charles W. Olsen, Ph.D.,Worldwide Technical Services Manager,Advanced Refining Technologies,Greg Rosinski, Technical Services Engineer andGeri D’Angelo, Senior Technical Services Engineer

28

N U M B E R 1 0 0N U M B E R 1 0 0 Fa l l 2 0 0 6

I n t h i s i s s u e . . .I n t h i s i s s u e . . .

Improvements in the PRISM process

Revolutionizing Gasoline Sulfur Reduction

Implications of Hydrogen on Coke

ur customers' success isa core value of GraceDavison and Advanced

Refining Technologies. Byworking in partnership withcustomers, we continue todevelop and commercializetechnology that not onlyensures their success, butleads the industry in innovation.

Grace uses a “stage and gate”process1 for new product devel-

opment called PrISM (ProductInnovation and StrategicMarketing) When we work withour customers to develop newproducts, we use this processto provide expeditious productevaluation and commercializa-tion by considering the techni-cal, as well as the businessobjectives of the refiner.

The PrISM Process is compre-hensive; it includes active par-

The PrISM Process for Product Development:

A Map for Customer-Driven R&D

O

(Research & Development)

www.e-catalysts.com2

byE. Thomas Habib, Jr.

Director, Customer Research

Partnerships, Grace Davison

Refining Technologies

STAGES ONGOINGBUSINESS

GATES

GATEKEEPERS

MERITREVIEW

FEASIBILTYREVIEW

NO-GO NO-GO NO-GO NO-GOHOLD

READINESSREVIEW

COMPLETENESSREVIEW

WRAP-UPREVIEW

Stage1Idea

Generation

Stage 2BusinessPlanning

Stage 3Development

Stage 4Commercial

Testing

Stage 5Commercialization

Marketing DirectorR&D Director

Marketing DirectorR&D DirectorDevelopment DirectorEvaluations Director

Marketing DirectorR&D DirectorDevelopment DirectorEvaluations DirectorManufacturing Director

Marketing Director(also signs off for sales)R&D DirectorManufacturing Director(also signs off for P&QA)

Figure 1

Catalagram 100 Fall 2006 3

ticipation from refiners and ourResearch and Development,Marketing, Sales and TechnicalService staff. This processmandates checks and valida-tion along the way for both tech-nical and business issues. Forexample, manufacturing per-sonnel are brought into theprocess early to avoid productand process designs that couldbe problematic on a commer-cial scale.

In the PrISM Process, projectsare conducted through stageswith various checkpoints wherethe decisions are made to con-tinue or cancel the project. ThePrISM Process consists of fivestages:

• Idea Generation• Business Planning• Development• Commercial Testing• Commercialization

Figure 1 shows the Stages, theGates and the Gate Keepers inthe FCC PrISM Process. Wewill explore each of these stagesin detail in order to provideinsight into the process of newcatalyst development and intro-duction for the optimum opera-tion of the FCCU in the refinery.

NEPTUNE™, Davison's newgasoline sulfur reduction cata-lyst, is a product of customer-driven R&D vetted through thePrISM process. This article willfollow NEPTUNE as it passesthe various stage-gates ofPrISM at Davison and its com-mercialization.

In developing NEPTUNE as apotential catalyst, and eventuallyas a commercial product, weused various Six Sigma tech-

niques through the stages ofthe PrISM process. Examplesof these techniques can beseen in Figures 2 and 3.

Customer Needs

Customer A

Customer Need 1

Customer Need 2

Customer Need 3

Customer Need 4

Customer Need 5

Customer Need 6

Customer Need 7

Customer B

Maximize, minimize or target

Functional Product Requirements

Impo

rtan

ce R

atin

g

Pro

duct

R

equi

rem

ent 1

Pro

duct

R

equi

rem

ent 2

Pro

duct

R

equi

rem

ent 3

Pro

duct

R

equi

rem

ent 4

Pro

duct

R

equi

rem

ent 5

Competitive Products

Customer Need 1

Customer Need 2

Customer Need 3

Customer Need 4

Customer Need 5

Customer Need 6

Customer Need 7

54671052

0309931

0100900

3000910

3100911

9099931

107867105

9031099

3303031

0300003

3000919

9999990

Relative Importance

Target Range

437 198 146 264 701

Figure 2Quality Function Deployment (QFD) is a tool used to capture

the voice of the customer in the ideation stage

Figure 3Design Of Experiment (DOE) is a statistical tool used to maximize

the usefulness of information extractedfrom a series of experiments

10

15

20Controlled

Variable

Temperature

20

25

0

50

100

Parameter A

Stage 1 - Idea Generation

Work in Stage 1 is geared toidentify the objectives for a newcatalyst.

This first stage, also known asIdeation, is driven by our cus-tomers. Routine sales calls,technical service assistance,seminars, and meetingsbetween customers and ourR&D professionals are all fertileground for ideas. Based on thisinput, Davison and the cus-tomer agree on what projectwould deliver the most value tothe customer and ultimately,the market.

A team of Grace experts,including Technical Service,Sales and Marketing, work withR&D to assign an R&D manag-er to the project, who thenbegins defining experiments to

understand the issue. Once thescope of the problem is under-stood, R&D shifts to preparingcatalysts to meet the challenge.

When a viable product concepthas been demonstrated , i.e., acatalyst has been prepared in thelaboratory that meets the goals,the project moves to a MeritReview.

At this point the Gate Keepersanswer the following questions:

• Does the catalyst meet the technical objectives?

• Can we make the catalyst?• Are there any absolute killer

variables (i.e. prohibitive raw material costs, unrea-sonable EHS issues, other yield effects, etc.).

• What is the timing and what are the resource demands to get through the next stage?

For NEPTUNE, the customers'objective was to develop a prod-uct that would reduce the sulfurcontent of FCC gasoline by 50%in a fully integrated catalyst.Such a product would help thesecustomers significantly in theirneed to reduce sulfur to 30 ppmin the refinery gasoline pool. OurR&D confirmed this product canbe made on lab scale to meet theperformance goals and we havedetermined we have the manu-facturing capability to produce it.

The customers who wanted thisproduct will buy it as long as itcan reduce sulfur levels in FCC

gasoline by 50% as long as itcan provide maximum gasolinesulfur reduction with noadverse effects on other prod-uct yields. We need to speedthe product to market within atwelve-month time frame tomake it a reasonable option forthese customers who need tobridge the gap until hardware isinstalled.

The NEPTUNE project passedthis phase, so a Project Leaderwas assigned and moved toBusiness Planning (Stage 2).The time required to completethe next stage is estimated anda date is set for the next gatereview (Feasibility Review).

Stage 2 - Business Planning

Work in Stage 2 is designed todetermine if the product con-cept could be made in a practi-cal manner.


FER

NO-GO

from Stage 1 to

Stage 3

FEASIBILTYREVIEW

Stage 2BusinessPlanning

Marketing DirectorR&D DirectorDevelopment DirectorEvaluations Director

ITR EW

HOLD NO-GO

to Stage 2

MERITREVIEW

Stage 1Idea

Generation

Marketing DirectorR&D Director

In Stage 2, our customer part-ners become even moreinvolved, as they are evaluatingthe new technology, along withDavison R&D, which conductsmore focused experiments todetermine the technical advan-tages of the new product andidentifies potential drawbacksin manufacturing. Intellectualproperty (IP) and environmen-tal, health and safety (EH&S)issues are investigated in thisstage.

At this point the Gate Keepersneed to answer the followingquestions:

• Is this product economicallyviable for both Grace and the customer?

• Will Davison be able to make this catalyst in our plant?

• Do we have or can we get the IP rights to make and sell this catalyst?

• What is the timing and whatare the resource demands to get through the next stage?

For NEPTUNE in Stage 2, dis-cussions were held with cus-tomer partners to determine thebest fit for the first commercialtrial. Preliminary raw materialswere defined and manufactur-ing process optimization isbeing determined. Since thereis no existing product in theindustry with similar perform-ance, a patent application willbe prepared and filed. An inter-nal review show there are noEH&S concerns regarding

product handling, shipping andmanufacturing, so an MSDSsheet is generated for NEPTUNE.

NEPTUNE now moved intoDevelopment (Stage 3). The timerequired to complete the nextstage is estimated and a date isset for the next gate review(Readiness Review). If there is akey milestone to be met partwaythrough Stage 3, a Status Updatewill be scheduled instead of aReadiness Review. The

Readiness Review would thenbe scheduled at that time.

Stage 3 - Development

Work in Stage 3 is focused inR&D on developing a plantprocess for making the product.

In Stage 3, a plant location isselected and appropriate scale-up experiments are conducted.EHS issues are paramount.Patents are filed as needed andthe Right to Practice will be ver-ified.

At the gate review, the projectteam will decide if there is suffi-cient data to show that the proj-ect is viable and a ReadinessReview is held. At this point thegate keepers need to answerthe following questions:

• Can we make this catalyst inthe plant for a reasonable cost without unacceptably disrupting operations?

• Do we have the IP rights to make and sell this catalyst and have we filed for appro-priate patent coverage?

NO-GO

from Stage 2 to

Stage 4

READINESSREVIEW

Stage 3Development

Marketing DirectorR&D DirectorDevelopment DirectorEvaluations DirectorManufacturing Director

NEPTUNE

True Conversion, lv.% +1.25

LPG Yield, lv.% +0.46

Gasoline Yield, lv.% +0.46

LCO Yield, lv.% -0.98

Slurry Yield, lv.% -0.27

Table INEPTUNE Trial


• What is the manufacturing cost and what is the timing required to ensure a successful commercial trial with our customer partner and ultimately bring the project to the general FCC market.

For NEPTUNE, a trial manufac-turing run at our developmentfacilities determined that for-mulation changes wererequired. Adjustments weremade, new components wereintegrated into the formulationand performance was con-firmed. The decision was madeto proceed with productionscale up and a patent applica-tion was submitted in the Fall of2004.

A customer partner has agreedto a trial at their FCCU startingin Fall 2005. Marketing hasdefined a price based on prod-uct value and standard margin.The decision was made to goforward with a commercialproduct consistent with the newformulation. Once again, NEP-TUNE passed this gate andmoves into Commercial Testing(Stage 4).

Theoretically, the time to com-plete the Stage 4 could be esti-mated and a date could be setfor the next gate review(Completeness Review).However, usually a StatusUpdate will be scheduled toreview the plant test results,and then another to review therefinery trial results. When suf-ficient commercial data is avail-

able, a Completeness Review isscheduled.

Stage 4 - Commercial Testing

The R&D work in Stage 4 consistsprimarily of plant support duringthe test run and pilot plant evalu-ations.

Davison FCC Marketing is respon-sible for coordination between ourcustomer, sales and manufactur-ing. They are also responsible forgetting feedback and data fromthe trial, as well as defining anyproduction issues in our plants.Based on trial results, the value ofthe product for the general mar-ket must be determined and a fullmarketing and manufacturingplan must be developed.

If the project team believes thereis sufficient data to show the proj-ect is viable, a CompletenessReview is held. At this point the

Gate Keepers need to answerthe following questions:

• Is this product viable for thegeneral FCC market?

• Are marketing/sales/manu-facturing plans in place forthe general market?

• Are there any lingering EHSor IP issues?

NEPTUNE's commercial trialwas held at the Corpus Christi,Texas refinery of CitgoPetroleum Corporation. Citgoplanned to start up a gasolinehydrotreater in Fall 2006 andthey wanted to reduce theirgasoline sulfur in the short termto comply with gasoline sulfurspecifications due to start inJanuary 2006. If the trial wassuccessful, they would useNEPTUNE until thehydrotreater start-up.

Results from Citgo's commer-cial data agree with Davison'sevaluation of submitted sam-ples. Both confirm the expect-ed results from the develop-ment phase. FCC gasoline sul-fur was reduced by an averageof 45% at constant gasolinecutpoint. Reductions of 58%were accomplished with under-cutting. Table I shows theimprovements in operation thatwere achieved in addition to thesulfur reduction.

Based on the successful trial atCitgo, NEPTUNE has now movedinto the final stage of the PrISMprocess: Commercialization(Stage 5). A Wrap-Up Review isscheduled for Fall 2006 to


NO-GO

from Stage 3 to

Stage 5

COMPLETENESSREVIEW

Stage 4Commercial

Testing

Marketing Director(also signs off for sales)R&D DirectorManufacturing Director(also signs off for P&QA)

address any new issues thatmay arise and the project isconsidered completed at thispoint.

Stage 5 - Commercialization

The work in Stage 5 consistsprimarily of the implementationof the marketing and manufac-turing plans for the general FCCmarket.

At the Wrap-Up Review theGate Keepers need to answerthe following questions:

• Are our customers satisfiedwith the catalyst perform-ance?

• Have we met all of the prod-uct quality specifications?

• Are the Patent, Right-to-Practice, and EHS issues allresolved?

At this point, the project is con-sidered completed and formallymoved out of the PrISMprocess. If any new issues havearisen, resources will beassigned to address them (usu-ally as plant support). If issues

are fundamental and unresolvedin the short term, a new PrISMproject may be initiated.

Due to the success of the NEP-TUNE operation at Citgo, CorpusChristi, Grace Davison has addedNEPTUNE to our vast catalystoptions for the refining industry.

The complete implementation ofthe PrISM Process is enhancedby the use of Six Sigma tools2. SixSigma is the disciplined, method-ological application of well-estab-lished statistical techniques toachieve a desired goal using asguidelines to “Define, Measure,Analyze, Implement and Control”and applying them to the processvariables. Companies haveshown dramatic improvements incommercial processes by theapplication of Six Sigma tech-niques.

We have confirmed that potentialreturns are even greater if theproduct or process can be opti-mized using Six Sigma methodsprior to commercial scale produc-tion. The use of our PrISMProcess in conjunction with SixSigma techniques has proven tobe an effective and powerfulmodel in commercializing cata-lysts efficiently, improving speedto market and ensuring that thefinal product meets the customerrequirements.

Conclusions

To effectively develop and com-mercialize customer-drive R&D,Grace Davison has implement-ed a structured, controlledprocess called PrISM. Theprocess, which includes stagesand gate keepers, assures thetimely introduction of new prod-ucts to the market with a highlikelihood of success both forthe customer partner andGrace Davison. The projectsare managed by cross-function-al development teams througha series of stages which aremarked by technical as well asbusiness objectives

References

1. R. G. Cooper, “Winning at NewProducts, Accelerating the Process fromIdea to Launch”, 3rd Edition, PerseusBooks, Reading, MA, 2001.

2. K. Rajagopalan, M. Francis and W.Suarez, “Developing Novel Catalysts withSix Sigma”, Research TechnologyManagement, January-February 2004.


ONGOINGBUSINESS

from Stage 4

WRAP-UPREVIEW

Stage 5Commercialization

race Davison, the industryleader in catalytic sulfurcontrol, announces break-

through catalytic technology forsulfur reduction in FCC gasoline:NEPTUNE, a fully flexible catalystwith industry-leading sulfurreduction functionality.

Introduction

In 1992, before the industrydefined a need for sulfur reduc-tion products, Davison anticipat-ed this potential market andbegan a strong commitment toresearch and development inFCC gasoline sulfur reduction.The objective of the work was tocultivate a family of FCC catalystsand additives to help refinersmeet clean fuels specifications.

Established technologies thatevolved from over 14 years of on-going effort include D-PriSM®,SuRCA® and GSR®-5. 1-3

At the beginning of 2006, strin-gent regulations on gasolinesulfur were implemented thataffect most US refineries. Tocomply with 30 ppm sulfur ingasoline4, refiners are forced tooperate in a window that is get-ting smaller and smaller. Acommercial trial at CitgoPetroleum's Corpus Christi,Texas refinery demonstratedthat NEPTUNE allows refinersmaximum flexibility with over45% FCC gasoline sulfur reduc-tion, giving them another optionfor achieving gasoline sulfurcompliance.

G

A New Generation Cracking Catalyst

Reduces Gasoline Sulfur by Nearly 60%

Neptune

(Sulfur Reduction)

byLauren A. Blanchard

Marketing Manager,Grace Davison



NEPTUNE Technology

In Fall 2005, when the Citgorefinery requested a minimumof 35% gasoline sulfur reduc-tion for one of their FCC units tokeep the refinery gasoline incompliance on sulfur, Gracerecommended our newly devel-oped NEPTUNE catalyst forthat application. Citgo, CorpusChristi elected to try the prod-uct, and began using it in placeof 100% of their fresh catalystadditions.

Previous generations of sulfurreduction catalysts (i.e., SAT-URN), showed gasoline sulfurreduction performance that wasdesirable to refiners, but werenot as cost competitive as otheroptions for reducing FCC gaso-line sulfur. Additionally, somerefiners who were sensitive togasoline octane and LPG olefinswould likely have seen a reduc-tion in both octane and olefinswith previous maximum sulfurreduction catalyst technologies.NEPTUNE was developed toprovide the formulation flexibili-ty needed to allow adjustmentsto the catalytic properties asnecessary to match the needsof any unit processing feedsfrom severely hydrotreated gasoil to heavy resid, while provid-ing a cost competitive meansfor the refiner to significantlyreduce gasoline sulfur.

Today Citgo, Corpus Christi suc-cessfully uses NEPTUNE withminimal undercutting to reducegasoline sulfur by up to 58%.In addition, gasoline selectivityincreased and other yieldsimproved.

Background

A road map for product selectionis shown in Figure 4. When for-mulating a plan for a customer,we consider the FCC gasolinestream targeted for sulfur reduc-tion, the desired level of gasolinesulfur reduction, and whether acatalyst or an additive is pre-ferred. Careful selection of theappropriate engineered solutionfor each application has resultedin consistent product perform-ance, which has led to Davisonsulfur reduction technologiesmeeting or exceeding customerexpectations. As a result, Gracecontinues to be the leader in pro-viding gasoline sulfur reduction tothe industry.

Today, Grace has combined over60 years of operating experiencewith successful gasoline sulfurreduction applications. For gaso-line sulfur reduction, refiners arechallenged more than ever beforeto blend various refinery streams

to meet stringent product spec-ifications and government regu-lations for clean air.

For refiners who desire FCCadditives for maximum operat-ing flexibility, Davison's D-PriSMadditive is most effective atreducing sulfur species in lightand intermediate FCC gasolineand has been used in morethan 25 refineries worldwide.D-PriSM has provided up to35% sulfur reduction on areduced endpoint FCC gasolinewith no FCC yield deterioration.

Grace's GSR-5 additive isbased on the SuRCA catalystchemistry, which provides 20-35% full range gasoline sulfurreduction.

The range of typical sulfur com-pounds found in FCC gasolinecan be seen in Figure 5. FCCgasoline samples sent to GraceDavison for analysis are testedfor sulfur species using a Gas

Preferred Technology

CATALYST

ADDITIVELight or Intermediate

Gasoline

Full RangeGasoline

Light & Intermediate

Solution

D-PriSM® 10-35%reduction

35%reductionor more

20-35%reduction

Light, Intermediate and Full range gasoline

NEPTUNE

GSR -5®

SuRCA

gasoline

Figure 4Clean Fuels Road Map


Chromatography AtomicEmission Detector (GCAED).The boiling point distributionshown in Figure 2 is that of theindividual sulfur compound andnot the gasoline distillation tem-perature (hydrocarbon boilingpoint). A gasoline with a 420°Fendpoint as measured by theD-86 distillation method couldstill have benzothiophene andheavier boiling sulfur speciespresent in appreciable concen-trations. The gasoline streamtherefore drives product selec-tion in a given application,including the distillation andsulfur species present in thestream. GSR-5, SuRCA andNEPTUNE effectively reducesulfur across the entire range ofgasoline sulfur species, evenreducing the ringed benzothio-phene and alkylbenzothio-phene type compounds, while

D-PriSM is best suited for specieslighter than benzothiophene.

Davison's SuRCA catalyst familyhas been designed to completelyreplace the conventional FCC cat-alyst in the circulating inventory,providing commercial levels of

gasoline sulfur reduction up to35%, while maintaining or evenenhancing existing yields andselectivities. There are over 40SuRCA applications worldwideto date, and 10 current usershave employed the technologyfor an average of over three

Cu

mu

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ve S

ulf

ur,

pp

m

Temperature, ˚F

800

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0

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D-PriSM SuRCA, GSR-5, NEPTUNE

Mer

capt

ains

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hylth

ioph

enes

Tetra

hydr

othi

ophe

ne

C2 T

hioph

enes

Thio

phen

ols

C3 T

hiop

hene

s

C4 T

hiop

hene

s

Benz

othi

ophe

ne

Alky

lben

zoth

ioph

enes

Thio

phen

e

Unid

entif

ied

S Co

mpo

unds

Figure 5Gasoline Sulfur Speciation Determined by Simulated Distillation

0

5

10

15

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25

30

35

40

45

# o

f A

pp

licat

ion

s

Length of Application

>100 Days >365 Days

Average Length forAll Sulfur ReductionApplications Worldwide

376Days

Longest Application(on-going)

Time

5.5Years

4021

Figure 6Davison Experience in Sulfur Reduction Applications


years. Additionally, reductionsof 10-20% in LCO sulfur havebeen observed in some applica-tions. Numerous refiners incor-porate SuRCA into their operat-ing strategies for long-termprofitability and operating flexi-bility.

To further expand our sulfurreduction technologies for con-tinuous improvements in bothperformance and cost effective-ness, Grace has recently com-mercialized a new gasoline sul-fur reduction catalyst family.This next generation technolo-gy, NEPTUNE, is a step outimprovement, providing 45-50% full range gasoline sulfurreduction commercially with fullcatalyst formulation flexibility.

Key statistics for all Grace sulfurreduction applications to datecan be seen in Figure 6.Davison is the establishedleader in the field of gasolinesulfur reduction experience, asis evident by the willingness ofrefiners to use Grace technolo-gies on a long-term, continuousbasis.

Commercial Trial at Citgo, Corpus Christi

The Citgo, Corpus Christi FCCunit processes 12,000 barrelsper day of 100% purchasedhydrotreated VGO. The unit is aUOP stack design that operatesin partial burn combustionmode. The refinery is commis-sioning a gasoline hydrotreaterin late 2006. Their objectivewas to assess the selected sul-fur reduction technology in late

2005 that would allow them tooperate in compliance beginningin January 2006 and continuinguntil the gasoline hydrotreatercame on-stream. Based on theperformance of the NEPTUNEtechnology in late 2005, Citgoelected to continue use of NEP-TUNE until the hydrotreating unitstarts up in 2006.

During the evaluation, FCC feedand gasoline samples were col-lected and analyzed so that gaso-line sulfur data could be correct-ed for feed sulfur changes.Analysis of NEPTUNE perform-ance was conducted using oper-ating data for the unit, as well asthe analysis of samples Citgo sup-plied to Grace. There is goodagreement between all analysismethods.

The operating data analysis issummarized in Figure 7. NEP-TUNE reduced all FCC gasolinesulfur species by an average of45% at constant gasoline cut-point. With undercutting, NEP-TUNE reduced gasoline sulfur bynearly 60%.

Utilizing the GCAED analysismethod, sulfur speciation forthe baseline gasoline samplesare shown in Figure 8. Eachsample is normalized for feedsulfur. The matching gasolinedistillation 95% point and end-point (by SIMDIST methodASTM D-2887) are shown foreach of the gasoline samplesanalyzed. Sample 8, during thebase period has the highest tailon the distillation. It then fol-lows that this sample containsthe highest concentration ofbenzothiophene, alkyl benzoth-iophenes.

Figure 9 shows the sulfurspecies results for the gasolinesamples collected during theNEPTUNE evaluation, normal-ized for feed sulfur. Selectingsamples from Figures 8 and 9that have similar distillation95% point and endpoints, andcomparing the amount of eachspecies present in the basesamples to the NEPTUNE peri-od, it is evident that gasolinesulfur reduction is significantacross all sulfur species. For

Figure 7Davison Experience in Sulfur Reduction Applications

1400

Gas

olin

e S

ulf

ur

No

rmal

ized

fo

r F

eed

Su

lfu

r

Base

NEPTUNE

46%reduction

44%reduction

58%reduction

355˚F D86 EP 475˚F D86 EP

1200

1000

800

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400

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0


12

34

56

78

0

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1 414 4902 414 4903 407 4754 407 4735 416 4826 435 5007 386 4408 442 508

Mercaptans

Thiophene

MethylThiophenes

TetrahydroThiophene

C2-T hiophenes

Thiophenol

C3-T hiophenes

MethylThiophenol

C4-T hiophenes

BenzoThiophene

C1-Benzot hiophenes

C2-Benzot hiophenes

SIMDIST 2887su

lfur,

pp

m

sample

Figure 8Base Period Gasoline Sulfur Speciation and Distillation

Mercaptans

Thiophene

MethylThiophenes

TetrahydroThiophene

C2-T hiophenes

Thiophenol

C3-T hiophenes

MethylThiophenol

C4-T hiophenes

BenzoThiophene

C1-Benzot hiophenes

C2-Benzot hiophenes

S l N b

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41

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61

7

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T95 FBP9 390 441

10 392 48711 389 44012 386 43913 387 44414 387 44115 393 44516 395 44717 388 44118 406 47419 417 572

SIMDIST 2887

sulfu

r, pp

m

sample

Figure 9NEPTUNE Period Gasoline Sulfur Speciation and Distillation


example, comparing samplenumber 4 in Figure 8 to sam-ple number 18 in Figure 9,NEPTUNE reduced all sulfurspecies by 25%. At the high-er end of the cutpoint range,comparing samples 8 inFigure 8 and 19 in Figure 9reduction across the speciesis 57%.

Performance of NEPTUNEexceeded expectations toCitgo’s high gasoline end-point. The endpoint, at 475˚F(D2887), has over 55% ben-zothiophene and heavier.Removing sulfur from theseringed species is a challengefor a catalytic technology.NEPTUNE achieved 44%gasoline sulfur reduction at a475˚F endpoint over the entirerange of sulfur species.

Citgo has also realized furtherimprovements in conversion,gasoline, and bottoms crack-ing with the use of NEPTUNE.Table II depicts the changesthe refinery observed with theNEPTUNE catalyst over theincumbent catalyst.

Conclusions

Grace Davison continues todevelop and commercializeFCC gasoline sulfur reductiontechnologies that are provento provide refiners with costeffective options to maximizeoperating flexibility. With theintroduction of our new, for-mulation flexible alumina-solbased catalyst technology ,FCC gasoline sulfur reductionin the range of 45-50% can

be achieved cost-effectively with-out sacrificing catalyst perform-ance, yields, or operating flexibili-ty. As a result of the perform-ance of NEPTUNE, Citgo, CorpusChristi will use the technology forthe majority of 2006 to help meetgasoline pool sulfur limits untiltheir gasoline hydrotreater iscommissioned.

Gasoline sulfur reduction cata-lysts and additives continue tofind applications in FCC units byproviding additional options andflexibility for meeting fuel specifi-cations while maximizing refineryprofitability. In virtually everyrefinery that needs to comply witha gasoline sulfur limit, gasolinesulfur reduction technologies canbe applied to achieve short-termand long-term operating objec-tives. Examples include:

• Improve economics as a result of extended FCC feed hydrotreater run length

• Maintain gasoline sulfur compliance when an FCC feed hydrotreater is down

• Process higher sulfur oppor-tunity feeds which cannot be normally handled by the refinery hardware con-figuration

• Increase refinery gasolineproduction by minimizing of FCC gasoline undercut-ting

• Comply with gasoline sul-fur specifications set by pipeline operators

• Preserve octane lost whenhydrotreating FCC naph-tha due to olefin saturation

• Reduce hydrogen con-sumption by reducing FCC naphtha hydrotreaterseverity

References

1. J. Balko, D. Sams and G. Krishnaiah,“Davison Clean Fuels TechnologyRefineries Report on CommercialPerformance”, Grace Davison CatalagramNo. 92, 2003

2. M. Gwin, E. Udvari and D. Hunt, “GraceDavison's SuRCA Catalyst Reduces FCCGasoline Sulfur and More at the Alon USA,Big Spring Refinery”, Grace DavisonCatalagram No. 96, 2004

3. S. Purnell, D. Leach and D. Hunt, “NextGeneration FCC Clean Fuels TechnologyBreaks Through 50% Gasoline SulfurReduction”, Grace Davison CatalagramNo. 90, 2002

4. EPA regulation, refinery average

NEPTUNE

True Conversion, lv.% +1.25

LPG Yield, lv.% +0.46

Gasoline Yield, lv.% +0.46

LCO Yield, lv.% -0.98

Slurry Yield, lv.% -0.27

Table IIImprovements realized with NEPTUNE


efiners often use hydrogenin coke as a parameter tojudge the performance of

their FCC catalyst stripper.However, the use of this parame-ter for process monitoring is oftenthe subject of significant debate.The main questions are whathydrogen in coke number trulyindicates good catalyst strippingand how valid is the numberitself.

I propose refiners use the hydro-gen in coke number to help con-firm the accuracy of their cokemake, other heat balance param-eters and flue gas analysis. Anyhydrogen in coke value less than5 wt.% or greater than 9 wt.% islikely due to poor flue gas analy-sis.

Use the Hydrogen in Coke Number toDetermine Coke Make Accuracy

by David HuntFCC Technical

Service Manager,Grace Davison


Since the flue gas analysis isthe basis for the heat balancecalculations, it influences manyof the calculated operatingparameters such as the unitcoke production, heat of reac-tion, catalyst circulation rate,and most dramatically, thehydrogen in coke. An artificiallylow hydrogen in coke numberresulting from an incorrect fluegas analysis will result in a cal-culated coke production fromthe unit that is higher than actu-al.

An accurate flue gas analysisand hydrogen in coke numberis especially important whenyou consider that manythroughput limitations are setby emission regulations based

(Analysis)


R

on coke production. Whenconsidering this, the use of thehydrogen in coke number tojudge stripping efficiencyshould be a secondary con-cern.

Calculating Hydrogen in CokePractical Limits

If your heat balance calcula-tions yield a hydrogen in cokeresult of 4 wt.% does this meanyou have a world-class stripper?Or if your hydrogen in coke is12 wt.% should you plan on astripper revamp during the nextturnaround? The answer toboth questions is likely “no”.

Generally the industry accepts5 to 6 wt.% hydrogen in coke asthe lowest attainable from idealstripping2. This is based on theassumption that if the FCCstripper performed perfectly itwould only allow coke consist-ing of highly unsaturated hydro-carbons to pass through to theregenerator.

In order to define the upper rea-sonable limit for hydrogen in

Coke Yield, w

t.% Fresh Feed

Rate, bpdAir, mscfmCO, ppmO2, vol.%

50,0001151002.0

Hyd

rog

en in

Co

ke, w

t.%

151413121110

987654321

13.0 13.5 14.0 14.5 15.0 16.015.5 16.5 17.0 17.5 18.0

CO2, vol.%

Hydrogen in Coke, wt.% Calculated Coke, wt.% Feed

6.5

6

5.5

5

4.5

4

-20.9579.05 (100-CO2-CO-O2) (O2+CO2+ CO)1

2A=

and regenerator flue gas CO2, CO and O2 units are mole % on a dry basis.1

Note that this equation is not accurate for units using supplemental oxygen.

Hydrogen in Coke, wt.%

= 100*AA+2.979*(CO2+CO)

where A is

Hydrogen in Coke can be calculated by the equation:

coke, you might consider a casewhere a substantial amount ofproduct is burned in the regener-ator. Burning the equivalent ofslurry oil (main fractionator bot-toms) in the regenerator as cokecould be considered an extremecase. In this circumstance, thehydrogen in coke would be ~ 9.0wt.%, which is the nominal hydro-gen content of a slurry oil with anAPI of ~ 01.

So, at best you may argue thatthe stripper produces coke witha hydrogen content of 5 wt.%and at an extreme case it mightproduce up to 9 wt.%. Dataoutside this range is likelyexplained by bad flue gas data.An inaccurate value of CO2 isoften the culprit; however, poorO2 results will cause errors inthe calculations as well.

The Influence of CO2 onHydrogen in Coke

Figure 10 shows the calculatedhydrogen in coke and cokeyield as a function of the meas-ured flue gas CO2 content for aFCC operating in full combus-tion with constant excess O2.Questionable data is indicatedby the dashed lines for hydro-gen in coke data outside of the5 to 9 wt.% range.

The impact of CO2 is significantand can affect not only the

Figure 10Influence of Flue Gas CO2 Value on Hydrogen in Coke and Coke Yield


hydrogen in coke value but per-haps more importantly the cal-culated coke yield. Figure 10suggests that coke yield couldbe off more than 10% due tobad flue gas data. Many FCCemission regulations, likeMACT II, are based on cokeproduction so accurate cokemeasurement is critical3.

The coke yield was calculatedusing the method described in

the Grace Davison Guide to FluidCatalytic Cracking, Part One4.

Next time you see a high or lowhydrogen in coke number in youroperating data, instead of imme-diately thinking about your strip-per performance, you may wantto check the validity of your fluegas analyses and realize that thereported coke yield (as well asother heat balance parameters)may be in error.

References

1. J. Deady, Interpreting Yield Estimates,Catalagram No. 82, 1991.

2. R. Sadeghbeigi, Fluid CatalyticCracking Handbook 2nd Edition, GulfPublishing, Houston, TX 2000, pg. 166.

3. National Emission Standards forHazardous Air Pollutants (NESHAP),40CFR63 Subpart UUU.

4. Grace Davison Guide to Fluid CatalyticCracking Part One,1993 pg.84-85.

Bob Bullard, Vice President and General Manager, now has direct responsibility for theRefining Technologies Americas commercial organizations. Bob will continue to serve asManaging Director, ART. In his new role Bob will focus on leveraging Davison's strongcustomer relationships and our market leadership within the refining industry.Reporting to Bob will be:Scott Purnell, General Manager North America, Refining TechnologiesRuben Cruz, General Manager Latin America, Refining TechnologiesAl Jordan, Director Sales Operations, Refining Technologies

John Creighton, Director of R&D, ART Charles Wear, Director of Sales, ARTJoanne Deady, Vice President, FCC Marketing and R&DJim Nee, Global Director, Strategic Business Relationships

Bob, who joined Grace in 1977, has held numerous manufacturing and sales management positions. He is aB.S.Ch.E. graduate of North Carolina State University and received an MBA from the University of North Carolina.

Joanne Deady has been named Vice President of FCC Marketing and R&D worldwide.Joanne will focus on accelerating our new products for Refining Technologies andextending our technological advantages. Joanne, who joined Grace in 1986 fromChevron, has held various technical and management postions in FCC Tech Service andMarketing. Most recently, she was Vice President and General Manager of Grace'sMembranes business. A B.S.Ch.E. graduate of the University of Delaware, Joanne holds anMBA from the Wharton School of the University of Pennsylvania.


People inthe

NEWS

Jim Nee has assumed the newly created position of Global Director Strategic BusinessRelationships - Refining Technologies. Jim will be responsible for strengthening customerfocus and growing the FCC business. Jim began his career with Grace Davison RefiningTechnologies, in Worms, Germany in March 1993, and held positions in research, develop-ment, sales and marketing. Prior to his current assignment, Jim was Director of FCCMarketing. Jim received his BSc in chemistry from Newcastle Polytechnic, England andwas awarded his Ph.D in chemistry by the University of Edinburgh, Scotlan

Silas Wong and Ron Naiser have joined the Refining Technologies Technical Sales forcein our Houston office. Silas, who was in sales for Davison's Discovery Sciences businessmost recently, joined Grace in 2001 as an FCC Technical Sales Representative. He is aB.S.Ch.E. graduate of Clemson University and holds a B.S. in biology from McGillUniversity. Ron joined Grace in 1994 in sales and technical services for our MolecularSieve product line, serving refiners, petrochemical plants and natural gas processors.Prior to joining Grace, Ron worked for eight years in UOP’s molecular sieve adsorbentsbusiness unit. Ron received his B.S. in Petroleum Engineering from Texas Tech University.

Chuck Olsen has become the Worldwide Technical Services Manager for AdvancedRefining Technologies. Chuck, who was previously ART's New Product Developmentmanager, has over 15 years of experience in hydroprocessing. He has held a variety oftechnical service, research and technical management positions in Chevron and GraceDavison before joining ART. Chuck holds a B.S.ChE degree from the University ofMinnesota, and M.S. and Ph.D. degrees in chemical engineering from the University ofIllinois in Champaign-Urbana.


Question No. 84: What is yourexperience for controlling FCCstack NOx emissions from partialburn operations? Please com-ment on low NOx CO boiler burn-ers, additive/catalyst applications,operating variable adjustmentsand flue gas NOx conversionequipment.

A: Generation of NOx in the par-tial burn FCC is one of the mostcomplicated and unit-specificphenomena that occurs.Nitrogen leaves the partial burnregenerator as molecular nitro-gen, nitrogen oxides, or reducednitrogen species, such as hydro-gen cyanide or ammonia. In theCO Boiler, each of these speciescan be oxidized, reduced, orremain unchanged, contributing

Answers toFCC Questions for 2006NPRA Q&APanel

to the final NO which isobserved at the FCC Stack. Inaddition, there are additionalNOx formation mechanismsthat take place directly in theCO boiler. These include ther-mal dissociation and reaction ofnitrogen and oxygen, directcombustion of nitrogen speciesin co-fired fuel gas and promptNOx formed via complex reac-tion between regenerator nitro-gen species and fuel gas hydro-carbon radicals.

Partial burn units often observea minimum in regenerator NOxemissions when running in alean partial burn (i.e. below 2%CO in flue gas). This resultswhen the NOx is produced inthe regenerator at low CO lev-

byDennis

KowalczykNational Technical

Sales Manager, Grace Davison



(Q&A)

els, but with a minimum ofexcess oxygen. However, asthe level of excess oxygen isconstrained, both the reducednitrogen species and theamount of unburned CO in theflue gas will increase, therebycreating conditions where NOxformation in the CO boilerbegins to dominate (Figure 84).

A retrofit of burner tips to “Low-NOx” burners can provide ben-efit to NOx emissions, particu-larly if the CO boiler in questionis in poor mechanical state.Observed reductions will be afunction of burning efficiency,mechanical design, andmechanical condition of the COboiler before the retrofit.

FCC Additives have shownsome effectiveness in partialburn situations. A recent com-mercial trial showed that forpartial burn units injecting plat-inum combustion promoter,switching to a low NOx combus-tion promoter can reduce stack

NOx. The use of a new GraceDavison additive provided addi-tional NOx reduction when com-bined with low NOx promoter.

A retrofit of downstream equip-ment for ammonia injection(SNCR) is often a very economi-cal method of controlling NOxemissions. Limitations on theamount of NH3 released to theenvironment (slip) as well as itseffects on downstream equip-ment must also be carefully con-

sidered. Other flue gas NOxconversion options includemodified flue gas scrubbingand SCR, which have bothbeen demonstrated to achievevery high levels of NOx reduc-tion.

Question No. 87: Some ZSM-5additives are designed to maxi-mize propylene productionwhile others maximize buty-lene. Describe the zeolitechemistry that is controlling C3

versus C4 selectivity.

A: Traditional ZSM-5 additiveshave been in use since the1980's where they were origi-nally employed to enhance theoctane value of FCC gasoline.Today, however, ZSM-5 addi-tives are primarily used toincrease the production ofpropylene and butylene fromthe FCCU (Figure 87a).

The ability of ZSM-5 to increaselight olefin yields is largely dueto the size and shape of itsmicropores. ZSM-5 comprises

Products

Feed (N, S)

CO2, COStack H2O

NOx, SOxO2, N2

Flue Gas

CO, CO2H2ONH3, HCNNOx?SO2H2S?, COS?HC’s?O2?, N2

Air

CO Boiler

In an FCCU operating in true partial burn stack NOx emissions can be reduced catalytically by converting reduced nitrogen species such as NH3 or HCN toN2 before they are burned to NOx in the CO boiler.

Figure 84

Feed

R

R

Cracking by Y-Zeolite and ZSM-5

Y-Zeolite

LCO

Gasoline

ButylenePropylene ZSM-5

PropyleneButyleneEthylene

Figure 87a


intersecting straight and sinu-soidal channels with smallerpore openings of around 5.5Angstroms. Such small poresallow the rapid diffusion andcracking of linear hydrocarbonswhile larger, more branchedhydrocarbons are too bulky toenter the pore system. Thisaccounts for the increase inFCC gasoline octane observedwhen ZSM-5 additives areemployed. Low octane linearhydrocarbons are cracked outof the gasoline (into LPGolefins) leaving the resultantgasoline richer in aromatics(and hence octane value.)ZSM-5 additives do not general-ly crack molecules boilingabove a typical gasoline end-point of 430˚F (Figure 87b).

The intrinsic activity of ZSM-5additives comes from a combi-nation of the number of alu-minum atoms in the zeoliticframework (Silica/Aluminaratio) and the effectiveness ofthe phosphorus stabilizationprocess. The Si/Al ratio of ZSM-5 can be varied from about 11

to infinity with a pure siliconframework. Studies have shownthat phosphorus stabilization canhave a profound effect on theresultant activity of the ZSM-5zeolite and this step of the addi-tive manufacturing process has tobe carefully optimized.

ZSM-5 typically cracks olefins inthe C6+ gasoline range. Sinceolefins cracking rates decreasewith molecular size, high ZSM-5activity is required to convertsome of the C6 olefins selectivelyto propylene. C7 olefins readilycrack into propylene andbutylenes. Reducing ZSM-5activity, therefore, is the usualroute to increasing the yield ofbutylenes relative to propylene asless C6 olefins are cracked. Thisactivity reduction is achieved byusing additives that contain ZSM-5 synthesized to a high Si/Al ratio,resulting in lower intrinsic activity.For a given crystal content, so-called butylenes selective addi-tives are less active comparedwith conventional propyleneselective additives because they

use low activity, high Si/Al ratioZSM-5 zeolite. Thus, higheradditive usage levels arerequired to achieve the desiredolefin yield, when operating inmaximum butylenes mode.

Recent research has shownthat it is possible to chemicallymodify ZSM-5 to increase thenumber of very strong acidsites. This results in more effec-tive cracking of C6 olefins topropylene. While the specificmodifications are proprietary innature, results have shownadvantages in not only propy-lene selectivity, but overall activ-ity as well. This new additivetechnology is currently in com-mercialization .

Question No. 88: How success-ful have refiners been in reduc-ing FCC naphtha sulfur levels inthe FCC riser and reactor?What levels of FCC naphthadesulfurization have youachieved? How do key reactionvariables affect FCC naphthasulfur levels? What types of cat-alytic technology are used forFCC gasoline sulfur reductionand what benefits have youachieved?

A: Refiners are achieving increas-ing levels of success in reducingFCC naphtha sulfur in the FCCriser and reactor. Dependingupon the strategy employed, sul-fur reduction in the range of10% to 30% is not uncom-mon, with recent technologyadvances pushing gasoline sul-fur reduction into the 45% to50% range.

2 3 4 5 6 7 8 9

Olefins Carbon Number

Ole

fin

Yie

ld (

wt.

%)

ZSM-5 cracks C6+ gasoline rangehydrocarbons to propylene and butylenes

BaseBaseBase

Base + ZSM-5Base + ZSM-5Base + ZSM-5

Figure 87b


To meet the demand for lowsulfur gasoline in the market-place, a significant number ofrefiners have implemented FCCfeed hydrotreating and/or oneof the process technologiescommercialized over the pastten years for FCC naphtha sul-fur reduction.

Those refiners not employingprocess or catalytic technologyare often forced to reduce theendpoint of the FCC naphtha,resulting in a reduction in therefinery gasoline pool volume(Figure 88a).

However, for those refiners whohave not as yet selected, con-structed or fully optimized agasoline desulfurization unit,catalytic technologies are beingemployed to bridge the gap.Generally, FCC naphtha sulfurreduction solutions have takenthe form of additives that areeither fed separately into theFCC unit or blended with the

fresh FCC catalyst. Typically,these additives provide FCCnaphtha sulfur reduction in therange of 10% to 30%. Thesetypes of additives can be used asan offset to lowering operatingseverity in the FCC gasolinedesulfurizer, thereby reducingoctane loss and increasing theoverall refinery gasoline blendingflexibility (Figure 88b).

Recently, Grace has introduceda new catalyst system for FCCsulfur reduction. The keyadvantage for this technologylies in the development of newchemistry and new manufac-turing techniques that improvedispersion of the active sites forsulfur reduction. Overall, thisapproach expands the potentialfor gasoline sulfur reductionsubstantially. One commercial

Figure 88a

0

5

10

15

20

25

30

35

40

45

50

100 150 200 250 300 350 400 450 500 550

Boiling Point (˚F)

Co

nce

ntr

atio

n (

pp

m)

Mercaptans

Th

iop

hen

e

Met

hylth

ioph

enes

Tet

rahy

drot

hiop

hene

C2-thiophenes

Thi

ophe

nol

C3-thiophenes

C4-thiophenes

Met

hylth

ioph

enol

Be

nzo

thio

ph

en

e

Met

hylb

enzo

thio

phen

e

S

R-SH

S R

R

SS

R

H

1-20% 30-55%30-50%

Alklylbenzothiophenes

0

100

200

300

400

500

600

700

800

100 150 200 250 300 350 400

Temperature (°F)

Cu

mu

lati

ve S

ulf

ur

(pp

m)

Me

rca

pta

ns

Th

iop

he

ne

Un

ide

ntif

ied

S C

om

po

un

ds

Me

thyl

thio

ph

en

es

Te

tra

hyd

roth

iop

he

ne

C2

Th

iop

he

ne

s

Th

iop

he

no

ls

C3

Th

iop

he

ne

s

C4

Th

iop

he

ne

s

0

1

2

3

4

5

6

7

8

9

75-100

100-125

125-150

150-175

175-200

200-225

225-250

250-275

275-300

300-325

325-350

350-375

375-400

Temperature (°F)

Ole

fin

s (w

t.%

)

Grace Davison products arehighly effective at reducing

gasoline sulfur species inlight gasoline range

Most of the olefins fall into the light gasoline.

Boiling Range Comparison: Gasoline Sulfur Species and OleÞns

Figure 88b


trial of this technology resultedin a 48% reduction in total FCCnaphtha sulfur.

The key FCC operating variableaffecting sulfur level in FCCnaphtha is the feedstock quali-ty, both the total sulfur contentand the hydrocarbon type. Twokey FCC operating variablesthat have an impact on naphthasulfur levels are the unit cellsize of the equilibrium crackingcatalyst and the FCC reactiontemperature. Davison studieshave shown that convertingfrom the lowest to the highestlevels of catalytic hydrogentransfer (characterized by high-er rare earth content and high-er unit cell size) results in FCCgasoline sulfur reduction rang-ing from 8% to 10%. Reducingreactor temperature is anothertool for reducing FCC naphthasulfur, although this strategy isoften limited by the desire toachieve optimum FCC operat-ing economics. Studies haveshown that FCC naphtha levelcan be reduced by 2% to 3%for every 10˚F drop in FCC reac-tion temperature.

Question No. 89: What are thecauses of catalyst fines deposi-tion in high velocity sections ofthe flue gas systems (orificechambers, third stage separa-tors, underflow nozzles, andexpander casings)? Are therespecific operating parametersor catalyst/additive propertiesthat are more likely to result infouling of this type?

A: Grace would agree that thesedeposits generally contain sodi-

um, calcium, aluminum and/orvanadium, often in sulfate formand usually containing sub-micron sized FCC catalyst fines.Inorganic contaminants intro-duced into the circulating inven-tory or into the flue gas system viaspray water quench may formmixed oxides that can melt atregenerator or flue gas tempera-tures. These molten oxidespotentially cause the surface offines to become sticky andadhere to each other and to sur-faces in the FCC regeneratorcyclones and flue gas system(Figure 89a).

Some of the inorganic com-pounds that have been identifiedin FCC expander deposits includesodium sulfite, potassium andaluminum sulfate, sodium bisul-fite, ammonium bisulfite, calciumsulfate and compounds contain-ing vanadium. Experience tellsus that units employing spraywater systems to quench the fluegas are often susceptible to such

fines deposition in high velocityzones in the flue gas system, soit is important that any spraywater contain minimal levels ofmineral content (Figure 89b). Itis possible that other sources ofinorganic oxides such as calci-um and sodium can be intro-duced into the FCC unit if cata-lyst is shipped to the refinery intrucks that are used for thetransport of other industrial rawmaterials. It is important to usea carrier that employs appropri-ate measures for preventingcross-contamination of FCCcatalyst with lime, cement andother industrial materials.

Since most of the fines collect-ed from deposits in high veloci-ty areas are less than 1 micronin size, it is important to mini-mize the generation of thesefines in unit via attrition. Forunits experiencing problemswith such deposits, it is criticalto use a low-attrition FCC cata-lyst based on an alumina-sol

Grace Davison Analyses of FCC Deposit

From Unit #1: Sintered Sub-Micron Catalyst Particles Glued Together By MetalSulfate Salts + Metal Sulfates Known to Combine With Vanadium Oxides toForm Low Melting Vanadates With MP As Low As 995°F

From Unit #2: Sintered Sub-Micron Catalyst Particles + Potassium AluminumSulfate

From Unit #3: Mostly Sodium Chloride

From Unit #4: Mostly Sodium Sulfite and Chloride / Iron From Corrosion

From Unit #5: Mostly Silica-Based FCC Catalyst

From Unit #6: Sodium & Ammonium Bisulfite with FCC Fines (<20 Microns)

From Unit #7: Calcium Sulfate and Sodium Aluminum Sulfuate

Figure 89a


binding system and to verifythat any potential high attritionsources in the regenerator havebeen identified and eliminated(Figure 89c). Minimizing 0 to40 micron content of the freshcatalyst can help as well. It isalso important that Third Stage(TSS) and Fourth Stage (FSS)Separation equipment be con-figured and operated properlyso as to avoid potential attritionsources. New expander bladedesigns are being implementedthat significantly reduce foulingrates.

Question No. 95: The mainfractionator bottoms slurry set-tler typically has a PSV for over-pressure protection. Is this PSVsized to relieve pressure fromwater vaporization that mightoccur during start-up as thesystem is heated up?

A: We need to be careful not tospeak to every design becausethere may be some differences

between designers (includingEPC piping designs), but in gen-eral the Slurry Settler ProcessSafety Valve (PSV) in a UOPdesign for example is sized forhydrostatic relief for a blocked-incase, or a fire case. Water vapor-ization from hot oil, either bywater being injected accidentallyor a low point pocket that is sud-denly exposed to hot oil, will mostlikely vaporize faster that a PSVcan respond.

The main safeguards are proce-dural. Cold oil circulation at start-up is performed to remove water,and low points are drained toremove water before heating thesystem. Operator training andcareful adherence to proper pro-cedure are critical.

Question No. 98: Have you triedrefrigerated cooling of main frac-tionator overhead vapor (after airand water cooling) to unload thewet gas compressor? For whatcircumstances would you recom-

mend refrigerated cooling?What is the lowest practicaloverhead receiver temperature?

A: At the exit of the overheadcondenser, the temperature ofthe FCC fractionator overheadstream is typically 250°F to350°F. This cooled vaporstream then flows to an over-head condenser where thegasoline and heavier compo-nents are condensed out as liq-uids (Figure 98).

For FCC units with insufficientoverhead condenser coolingcapacity, problems may beexperienced with high tempera-ture and pressure throughoutthe overhead system. Higherthan desirable temperature willresult in less than optimal con-densation of liquid in the con-denser receiver. Optimum tem-perature for C5 equilibrium istypically in the range of 100°Fto 110°F. Minimizing theamount of C5 hydrocarbon inthe compressor inlet streamallows for maximum capacityfor C4 and lighter compression.

This problem can be addressedby supplementing the coolingwater on the overhead con-densers with chilled water tolower the exit temperature ofthe fractionator overheadstream. As an alternative, it isoften possible to configure thechilling unit so that rather thanchilling water in the coolingloop, hydrocarbon is chilleddirectly. In one application, 300gallons per minute (GPM) ofhydrocarbon was circulated

Turbine Expander Vibration Data

8/12/00 10/01/00 11/20/00 01/09/01 02/28/01 04/19/01 06/08/01

7

6

5

4

3

2

1

0

Date

Time between cleaning cycles increased

Start Date forAURORA-LLI

Figure 89c


from the bottom of the con-denser receiver through thechiller. The temperature of thishydrocarbon stream wasreduced from 120°F to 60°Fand the stream was recycledback to the inlet of the receiver.By implementing direct coolingof the receiver liquid, tempera-ture of the liquid in the receiverwas reduced from 120°F tobelow 100°F. Using the directcooling configuration requiresonly half of the equipmentrequired for indirect cooling viachilled water circulation. It isgenerally recognized thatreceiver liquid temperatureshould not drop below about70˚F in order to prevent lowmolecular weight compressorfeed and downstream fouling.

The primary benefit of reducingoverhead condenser receivertemperature results from opti-mization of C5 condensationand recovery. This results inefficient performance of the wet

gas compressor and eliminatesthe impact of high C5 content onthe FCC recovery section heatbalance.

Chilled water has been used toenhance the cooling on the over-head condenser stream on propy-lene splitting columns on fluidcatalytic cracking units. Toaccomplish this, a slip stream iswithdrawn from the reflux accu-mulator and chilled, then recircu-lated back to the top of the refluxaccumulator. In one case, therecovery of propylene doubled bymaintaining the temperature ofthe reflux drum 20 degrees lowerthan normal.

Question No. 106: What are thetypical phenol levels in the sourwater from a FCCU and how canthe phenol be minimized?

A: The FCC unit produces phenolin the cracking regime of thereactor riser by two primaryroutes. The first is from cracking

feed molecules that naturallycontain oxygen bonded to thearomatic structures. Generally,the largest contributor to FCCphenol production is the naturaloxygen content of the feed-stock. This is often evidentwhen phenol levels in FCC sourwater are reduced by a factor of2 to 3 times upon implementa-tion of FCC feed hydrotreating.

The second source of phenolproduction in the FCC unit isfrom reaction of hydrocarbonwith extraneous oxygen sourcesin the cracking zone. Thesewould include any atmosphericoxygen dissolved into the feedduring storage, air purges usedon the FCC reactor or regenera-tor and combustion gasesentrained with the regeneratedcatalyst. In order to minimizethe creation of phenols in theFCC riser, it is important to min-imize the entrainment of oxygenin the circulating catalyst and toreduce the opportunity for theFCC feed to interact and poten-tially dissolve air during storageand transfer (Figure 106).

Once formed, much of the phe-nol is subsequently washed outof the hydrocarbon phase viathe water wash system and thusleaves the FCC unit with thesour water from the main col-umn overhead receiver. Thelevel of phenol present in theFCC sour water generallyranges from 50 to 450 ppm,with 100 to 200 ppm being typ-ical. Refiners can affect wherethe phenol is removed up byadjusting the heavy gasoline

FCC Main Column Overhead System

WGC1st Stage

InterstageDrum

WGC2nd Stage

Main ColumnReceiver

MainColumnHigh Pressure

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ToStripper

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Figure 98


cut. Some refiners report thatraising the heavy gasoline cut-point reduces phenol in thesour water.

One method previously report-ed for limiting phenol dischargeis to send the stripped waterfrom the sour water stripper tothe crude distillation unit foruse as wash water. Some of thephenols in the water will parti-tion into the hydrocarbonstreams in the crude distillationunit. Other refiners sendstripped sour water to thedesalter to recover as muchphenol as possible into thecrude oil. However, a majorconcern is that pH can begreater than 7.5, potentiallyleading to more stable emul-sions in the desalter.

Our friends at Baker Petrolitetell us that when a tank of highphenol sour water can be isolat-ed, it can be treated with potas-sium permanganate to destroythe phenol. If there is a highcontinuous level of phenol,there are acclimated bacterialcultures available that areadapted to metabolizing highlevels of phenol. TheseChemcrobes have been utilizedsuccessfully in refineries in anumber of countries. Whenutilizing microbes capable ofhandling higher levels of phe-nol, it is important to store sourwater to feed the waste waterplant during FCC shutdowns.

Question No. 113: For ResidFCC units converted to opera-tion with lighter feeds, what

options are available to preventregenerator temperature fromdropping below acceptable lev-els? What are the operating andeconomic considerations for eachoption?

A: Options for increasing regener-ator temperature with lighterfeedstocks have been well-docu-mented in the Q&A sessions overrecent history. Practical optionsinclude recycle of slurry oil,reducing the amount of strippingsteam to allow more product toflow to the regenerator, increasingfeed preheat temperature anduse of a cracking catalyst thatproduces more catalytic coke perunit of conversion. Another pos-sibility is controlled addition ofsome vacuum tower bottomsback to the feed. As always, theoptimum approach for any FCCunit will depend on the specificoperating constraints for that unit.Each of the options is discussedbelow with a set of key considera-tions (Figure 113).

Recycling slurry with gravity of10 or less will certainly increasethe regenerator temperature,but will only provide a slightincrease in conversion. Very lit-tle of the slurry will convert togasoline, while the yield of ther-mal product (coke, dry gas andsome LPG) will increase andthere could be a slight loss ingasoline octane. As a rule-of-thumb, for each barrel of slurryrecycle added to 100 barrels offresh feed, coke yield willincrease by about 0.05 wt.%and regenerator temperaturewill heat up by 5˚F to 6˚F. Theresulting increase in total FCCproduct value will only increaseby a few pennies per barrel.

Reducing the rate of strippingsteam within the normal operat-ing range of a typical strippersteam ring will increase the flowof entrained product to the FCCregenerator and increase theregenerator temperature by20˚F to 30˚F. This approach

Options For Minimizing Phenol in FCC Sour Water

Reduce High Oxygen-Containing FeedHydrocarbons

Minimize Oxygen Entrainment in CatalystCirculation

Prevent Air Capture in Feed During Transfer &Storage

Increase Heavy FCC Gasoline Endpoint

Use Stripped Sour Water as Crude Unit WashWater or Desalter Water – Watch the pH

Use Specialized Chemcrobes to MetabolizePhenol

Figure 106


has three key drawbacks. First,the mechanical integrity ofstripper steam rings can becompromised if the rate turn-down allows catalyst to enternozzles, either plugging por-tions of the ring or causing ero-sion to occur. Second, withincreased hydrocarbon loadingto the regenerator, it may bemore difficult to maintain car-bon-on-regenerated catalyst atthe desired level, therebyreducing catalytic activity. Andthird, sending the spent catalystto regeneration with morehydrocarbon entrained willresult in higher internal catalysttemperatures during initialcombustion, resulting in anacceleration in catalyst deacti-vation and either loweractivity/conversion or a highercatalyst replacement rate.Neither of these possibilities willenhance FCC profitability.

Increasing feed preheat tem-perature will usually increaseregenerator temperature byslowing down catalyst circula-tion, unless the stripper is oper-

ating at inefficiently high rates. Ifriser temperature is held con-stant, raising the feed preheattemperature by 100˚F will slowdown the circulation of catalystand on average, will increaseregenerator temperature by 15˚Fto 20˚F. This increases the ratioof thermal to catalytic cracking,resulting in up to a 10% increasein dry gas and a 1 to 1.5 numberdrop in conversion. With 100˚F inincreased feed temperature, totalper barrel FCC product valuecould drop by as much as 4% to5%.

Increasing equilibrium catalystactivity will raise regenerator tem-perature. This can be accom-plished either by increasing baseactivity of the fresh catalyst or byincreasing the fresh catalyst addi-tion rate. If the need forincreased regenerator tempera-ture is ongoing, rather than inter-im, then increasing the baseactivity of the fresh FCC catalystwill usually be more economical.In addition, higher activity freshcatalyst will result in more con-taminant metals on the equilibri-

um catalyst, thereby adding tocoke make and adding toregenerator temperature. For atwo number increase in freshcatalyst activity, regeneratortemperature can be expected toincrease by 10˚F to 12˚F andconversion will increase byabout 1.0 vol%. Increasingequilibrium catalyst activity isgenerally the most profitableoption for increasing FCCregenerator temperature.

The premise for this questionassumes that the refiner justtransitioned the FCC unit tooperating with a lighter feed,thereby implying that heavierstreams were purposely divert-ed from the FCC feed blend.Therefore, it may not be possi-ble to isolate a few barrels ofvacuum tower bottom and sendthose to the FCC. But if it ispossible, adding some residbarrels back to the FCC is gen-erally more profitable thanadding slurry recycle.Depending on the quality of theresid, C3 to 650˚F liquid yield ofup to 90% can be achieved forthe incremental resid barrel.

Options For Increasing RegeneratorTemperature With Lighter Feeds

Recycle of Low API Gravity Slurry

Reduce Stripping Steam Rate

Increase Feed Preheat Temperature

Increase FCC Catalyst Activity

Often the Most Profitable Option

Add Some VTB to the Feed

Figure 113



Grace Davison environmental technologies have helped refiners reduce FCCU emissions

for over a quarter of a century.

The FCCU is often the largest point source within the refinery for SOxand NOx emissions. The use of innovative catalytic technologiesreduces emissions from the FCCU regenerator, without the need forcapital intensive “end-of-pipe” hardware solutions.

Super DESOX® provides industry leading SOx removal effective-ness. More and more refiners are finding that Super DESOX cancost effectively control SOx emissions below 25 vppm from a widerange of uncontrolled SOx baseline emissions.

Grace Davison researchers have studied the complex forma-tion of NOx and developed two additives to reduce NOx.XNOx® is a low NOx combustion promoter designed toreplace conventional promoters, which often causeincreased NOx formation. For units not using a promoter,or requiring additional NOx reduction, DENOX® is theadditive of choice. NOx reductions in excess of 50%have been observed commercially with both products.With more than 50 commercial applications of NOxadditives, Davison has more experience than the restof the industry combined and would be happy toassist you in reducing FCCU NOx emissions.

Extensive customer-driven research efforts at Grace are providing new insights into improvingSOx and NOx removal. Want to find out more about our environmental technologies? Contact us at www.e-catalysts.com or call us at (410) 531-8226.Let Grace Davison help you meet your FCCU emission challenges.

Your proven FCCU emissions solution.Grace Davison:

dvanced Refining Tech-nologies (ART) first intro-duced the ApART Catalyst

SystemTM for superior FCC feedsulfur reduction and FCC feedupgrading in 2002. Since thattime the technology has beenwidely accepted by the industry.As detailed previously (CatalagramNo. 91, 2002), the performance ofthe technology is driven by ARTAT575 and AT775, catalysts whichhave been specifically designedfor FCC feed processing.

by Greg Rosinski

Technical ServicesEngineer,

Geri D’AngeloSenior Technical

Services Engineer,and

Charles OlsenWorldwide Technical

Services Manager

The ApART catalyst technologywas developed to provide signif-icant improvements in HDSactivity AND provide significantupgrading of FCC feeds (i.e.nitrogen removal, PNA satura-tion). This technology has beena great success since its intro-duction just a few years agowith millions of pounds installedin commercial units. The firstrefiner to utilize the ApARTtechnology is still enjoying itsbenefits today, a good demon-stration of the exceptional sta-

ApART Catalyst SystemTM Excels in Commercial Service: Update on Advanced Pretreating by ART


A

(Technology Update)

bility of the system. In 2005,ART announced a new additionto the ApART portfolio, AT792.This newest catalyst compo-nent is already in service in twounits in North America, anddemonstrates ART's commit-ment to providing state-of-the-art technology for FCC pretreat-ing and VGO desulfurization.

What follows is a summary ofselected case studies whichhighlight the performance ofthe ApART catalyst system in avariety of FCC pretreat unitsaround the world.

Figure 11 shows the perform-ance of an ApART system at amajor West Coast refinery. Thisrefiner selected the ApART sys-tem for their FCC feed pre-treater based on testing resultswhich demonstrated the highactivity of the technology com-pared to competitive offerings.The unit operates at a LHSV ofaround 2, an HDS conversion ofabout 89% and a typical run

length of 12 months. As can beseen in Figure 11, the stability ofthe ApART system has beenquite good with a deactivationrate for the cycle of only about2.6°F/month.

This refiner noticed that the sta-bility and activity of the ApARTsystem were an improvementover previous cycles. In fact, thedifference was large enough thata significant amount of catalyst

activity would remain at the endof the 12 month cycle.Recognizing this, the refinerhas been increasing the severi-ty of the operation in terms ofsulfur conversion and FCC feedupgrading in an attempt to useas much of the activity as possi-ble before the planned turnaround. They have a con-straint around the FCC whichlimits the allowable sulfur con-version, but even with that theywere able to decrease productsulfur from about 0.22 wt.% to0.17 wt.% while the APIincrease went from around 4.0to 4.5 during the last part of thecycle. Despite the increasedseverity of operation it appearsactivity will still remain at theend of the cycle prompting thisrefiner to comment that this isthe best cycle they have hadwith this unit.

Figure 12 summarizes theexperience of a major EastCoast refiner who selected an

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Figure 12ApART Performance for Refiner 2


ApART system for their FCCfeed pretreater in 2005. This isa low pressure, high LHSV unitwhich also happens to have ahydrogen limitation. The unitobjectives are high sulfurremoval and maximum APIupgrade within the constraintsof the hydrogen limitation. ARTperformed in house testing tooptimize the NiMo/CoMo ratioof the ApART system to meetthese goals.

The unit has been on-line fornearly 12 months and the cata-lyst performance has beenexcellent. Figure 12 summa-rizes both the actual WABT andthe normalized WABT for thisoperation. As seen in the fig-ure, the actual WABT for theunit is quickly ramped up tomaximize the API upgrade (i.e.maximize PNA saturation).The normalized WABT showsthat they are overtreating with

respect to sulfur at these condi-tions. The deactivation rate indi-cated by the normalized tempera-tures is 2.5-3.0°F/mo. Figure 13summarizes the quality of theFCC feed for the cycle thus far.The sulfur levels are quite low andthe API upgrade easily exceedsthe target of 1.5 numbers. This

client has also indicated thathydrogen consumption is 5-10% lower with the ApART sys-tem compared to competitorproducts in the previous cycles.Needless to say, the client ispleased with the performance.

Figure 14 summarizes the per-formance of an ApART systemin Latin America which startedup in the first half of 2005. Theobjective of this FCC pretreaterwas to achieve >74% desulfur-ization for a cycle length of twoyears. This unit processes avery difficult feed which is highin sulfur and nitrogen, and inaddition, the unit does not havean amine scrubber so the recy-cle gas has a high concentra-tion of H2S; the H2S contenthas varied from 6 to 18 mole%with the average for the cycleapproximately 10 mole%. Thatlevel of H2S impacts activity andrepresents about 25-50°F oflost activity.

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Figure 13FCC Feed Quality for Refiner 2

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Nonetheless, as can be seen inFigure 14, the ApART systemhas shown exceptional activityand stability. The observeddeactivation rate is only about3.7°F/month, and even thoughthis unit is run to a sulfur targetit still achieves about 4 numberimprovement in API on aver-age. The catalyst system is ontrack to exceed the desired runlength by about 12 months ormore.

One of the first applications forthe ApART system was at aMidwestern refinery starting inSpring 2003. The goal of theunit was to achieve at least 70%desulfurization for a minimumof 18 months. The challengewith this unit was extremely lowH2 partial pressure due to thecombination of low unit pres-sure and low hydrogen puritywhich approached 60 mole%.Compressor problems resultedin lower than expected treatgasrates which steadily declinedduring the cycle. The bottom

line was that the hydrogen partialpressure averaged only 350 psiaover the first 400 days of thecycle until the compressor wasshutdown for repairs. Afterrepairing the compressor, thetreat gas rate doubled from thestart of the cycle. Figure 15shows how the hydrogen to oilratio varied through the course of

the run. As can be seen in thefigure, for several months theH2/Oil was barely above 400SCFB.

In spite of these poor condi-tions, the ApART system pro-duced on specification productin terms of sulfur while alsoachieving 1.5 number increasein API. Figure 16 shows howthe normalized WABT changedduring the run. Note the periodduring the middle of the cyclewhere very little deactivation isseen, and this corresponds tothe period when the H2/oil ratiowas at its worse. The unit waseventually shut down due toscheduled maintenance in therefinery even though there wasstill catalyst activity remaining.

A Far East refiner has beenusing an ApART system sinceearly 2005 for their VGOhydrotreater. The unit LHSV isjust over 2, and the H2/Oil is low

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at just over 1000 SCFB. Thefeed is difficult with about 2wt.% sulfur and an endpointapproaching 1200°F with occa-sional spikes to 1300°F. Thefeed also contains a relativelyhigh level of Ni+V. Spent sam-ples from the previous cycleshowed that AT510, ART's VGOdemetallation catalyst, pickedup 25 wt.% Ni+V. Despite thesevere feed and operating con-

ditions the ApART system is pro-viding excellent performance.Figure 17 summarizes the opera-tion to date. The deactivation ratesuggested by the normalized datain the figure is only 1.6°F/month.This refiner has indicated that thisis the best run they have had, andthey selected another ApARTsystem for the next cycle basedon the impressive performanceexperienced in this cycle.

As these cases demonstrate,the ApART catalyst system hasdemonstrated that a staged cat-alyst approach provides superi-or performance in terms of HDSactivity and FCC feed upgrad-ing. In addition to providinghigh activity, ART's catalysttechnology has shown superiorstability in even the mostadverse feed and operatingconditions. This has enabledrefiners to enhance profitabilitythrough improved FCC per-formance and lower FCC prod-uct sulfur levels. AdvancedRefining Technologies contin-ues to work to develop higherperformance products for FCCpretreating, and through itsunique relationship with GraceDavison Refining Technologies,offers a better understanding ofthe FCC pretreater and itsimpacts on FCC performance.

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Have questions about our clean fuels technology? Contact us at www.e-catalysts.com or call us at (410) 531-8226.

Let Grace Davison and Advanced Refining Technologies give you the custom catalytic solution to your clean fuels challenges.

Your Clean Fuels Solutions

For gasoline sulfur reduction, today's refiners are challenged morethan ever before to blend various refinery streams to meet stringentproduct specifications and government regulations for clean air.Proven in over 75 commercial units, Grace Davison's portfolio ofFCC gasoline sulfur reduction technologies includes the D-PriSM®

and GSR®-5 additives and the SuRCA®, SATURN® and GSR®-7catalyst families.

>Recently commercialized, GSR-7 catalyst further expands oursulfur reduction technologies to continuously improve both per-formance and cost effectiveness. This next generation technolo-gy is a step out improvement over earlier technologies, providing45-50% full range gasoline sulfur reduction commercially withfull catalyst formulation flexibility.

>For refiners with FCC pretreaters, the ApART Catalyst System™utilizing combinations of ART AT575, AT775 and AT792 offers theopportunity to significantly increase sulfur removal in thehydrotreater while at the same time maximizing FCC feed quality. Theimproved performance of the pretreater results in higher gasolinepotential in addition to decreasing FCC gasoline sulfur.

>For ULSD processing, the SmART Catalyst System™ utilizes state-of-the-art catalyst technology which is staged in the properproportions to provide the best performance, while at the sametime meeting individual refiner requirements. The catalyst stag-ing is designed to selectively take advantage of the different reac-tion mechanisms for sulfur removal with efficient hydrogen usage.ART CDXi, our newest generation of high activity CoMo catalyst,efficiently removes the unhindered, easy sulfur via the directabstraction route, while ART NDXi, our high activity NiMo cata-lyst, then attacks the remaining sterically hindered, hard sulfur.The SmART system provides higher activity than either the tradi-tional CoMo or NiMo catalyst alone while effectively helping therefiner manage hydrogen utilization.

When it comes to commercially proven technology to meet increasingly stringent

Clean Fuels regulations, make Grace Davison and Advanced Refining Technologies

your one-stop shop for FCC catalysts, additives and hydroprocessing catalysts.

N U M B E R 1 0 0 Fa l l 2 0 0 6

Davison Ref in ing TechnologiesW.R. Grace & Co.-Conn.7500 Grace Dr iveColumbia , MD 21044(410) 531-4000

Davison Ref in ing TechnologiesAsia Pac i f icW.R. Grace Pte. Ltd.501 Orchard Road#05-11/12 Wheelock PlaceSingapore 238880(65) 6737-5488

Davison Ref in ing Technologies Europe Grace GmbH & Co. K.G.In der Hol lerhecke 1Post fach 1445D-67545 Worms, Germany49 (6241) 40300

cata [email protected]

©2006 W.R. Grace & Co.-Conn.

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