Catalagram®

ARefining Technologies Publication

Issue No. 107 / 2010 / www.grace.com

In this issue

• GENESIS® Catalyst Commercial Update

• Distillate Pool Maximization by Additional Hydroprocessing

• Salt Deposition in FCC Gas Concentration Units

• CP® P - Third Generation Low NOx CO Promoter

Dear Refiners,

The current refining atmosphere in North American andEurope is the most difficult in over a quarter century.Declining utilization rates, narrow light-heavy differentials,and weak demand for transportation fuels has meantsteeply declining profitability for refiners.

As the leading supplier of FCC catalysts and additives,Grace Davison is dedicated to helping you navigate thisturbulence. Our investment in world-class research anddevelopment to constantly invent new products and fine-tune existing ones continues strong in this challengingenvironment. With our flexible technology base and broadmanufacturing capabilities, we deliver the catalyst solu-tions you need to be profitable and the value you deserve.

This issue of the Catalagram® highlights the successful application flexibility of our GENESIS® solutions to ourcustomers' challenge of the need to react quickly to changing supply/demand dynamics. These catalysts havebeen custom blended in 80 applications for over 50 refineries worldwide. As product slate demand changes,GENESIS® catalyst in the unit can be reformulated to maximize profitability and capture short term economicopportunities. To speed implementation, formulation adjustment can take place in the fresh hopper, minimizingthe delay often associated with a catalyst change out.

We also introduce our third generation non-platinum low NOx CO promoter, CP® P. Our newest CO promoterdelivers quick CO/afterburn response, equivalent to traditional platinum formulated promoters, and up to 20%lower NOx emissions compared to competitive products.

On the immediate horizon, we introduce our new products AsteraTM and AlcyonTM. Units that are circulation limit-ed can’t take full advantage of improved feed quality. When the FCC catalyst is not active enough regeneratortemperatures become too low and desired reactor temperatures can’t be achieved. Some refiners resort toburning torch oil or recycling slurry to provide additional delta coke which is often detrimental to the operation.With its novel, unconventional silica-alumina binder, AsteraTM FCC catalyst not only delivers excellent value butwill improve your yield slate and reliability. Best of all, AsteraTM will lower your daily catalyst cost. AlyconTM is arevolutionary new FCC catalyst designed for the maximum activity needed to process hydrotreated feeds. Lookfor more information from us in the coming months.

Our responsibility to our refining customers is the core of our business. We pledge to continue developing theproducts and services that will maximize your profitability in all economic climates.

Joanne DeadyVice President, Global MarketingGrace Davison Refining Technologies

A MESSAGE FROM THE EDITOR...

GRACE DAVISON CATALAGRAM 1

Managing Editor Joanne Deady and TechnicalEditor Rosann Schiller

04 Grace Davison’s GENESIS® Catalyst SystemsProvide Refiners the Flexibility to CaptureEconomic OpportunitiesBy Rosann K. Schiller

GENESIS® is one of Grace Davison’s most successful catalysts,with 20% of the world’s FCC capacity, having utilized the technology.GENESIS® systems offer refiners formulation flexibility and the abilityto realize the desired yield shifts quickly in order to capture dynamiceconomic opportunities.

13 Development of Next Generation Low NOxCombustion Promoters Based on NewMechanistic InsightsBy Eric Griesinger, Mike Ziebarth and Uday Singh

Grace research and development efforts have led to the develop-ment of CP® P, a new low NOx combustion promoter. Data frommultiple field trials has indicated excellent CO control with quickresponse to afterburn and/or CO excursions, like traditional Pt-based promoters. However, unlike traditional promoters, CP® P pro-vides lower NOx emissions and very quick NOx emission decayperiods.

22 Distillate Pool Maximizationby Additional LCO HydroprocessingBy Brian Watkins, David Krenzke and Charles Olsen

Advanced Refining Technologies® has developed catalysts specifi-cally designed to handle more difficult feeds exemplified by theSmART Catalyst System® technology for ULSD. This technologyhas been widely accepted, with over 75 units in commercial servicesince its inception. ART continues to improve its line of ultra highactivity ULSD catalysts with the addition of an SRO catalyst.

34 Salt Deposition in FCC Gas ConcentrationUnitsBy Michel Melin, Gordon McElhiney and Colin Baillie

Various operational problems can arise when salt deposition occursin FCC gas concentration units. Grace Davison Technical Servicetroubleshoots users of alumina sol catalysts to manage and solveany issues of ammonium chloride deposition.

IN THIS ISSUE

Catalagram 107ISSUE No. 107 / 2010

Managing Editor:Joanne Deady

Technical Editor:Rosann Schiller

Contributors:Colin BaillieEric GriesingerDavid KrenzkeGordon McElhineyMichel MelinCharles OlsenRosann SchillerUday SinghBrian WatkinsMike Ziebarth

Please address your comments to:betsy.mettee@grace.com

Grace Davison RefiningTechnologiesAdvanced Refining Technologies7500 Grace DriveColumbia, MD 21044410.531.4000

www.e-catalysts.comwww.grace.comwww.artcatalysts.com

© 2010

W. R. Grace & Co.-Conn.

Catalagram®

ARefining Technologies Publication

Issue No. 107 / 2010 / www.grace.com

In this issue

• GENESIS® Catalyst Commercial Update

• Distillate Pool Maximization by Additional Hydroprocessing

• Salt Deposition in FCC Gas Concentration Units

• CP® P - Third Generation Low NOx CO Promoter

GRACE DAVISON CATALAGRAM 13

Eric Griesinger

Product Manager

Environmental Additives

Grace Davison

Refining Technologies

Columbia, MD

Mike Ziebarth

Manager

Synthesis Research

Grace Davison

Refining Technologies

Columbia, MD

Udayshankar G. Singh

Research & Development

Engineer

Grace Davison

Refining Technologies

Columbia, MD

The use of low NOx combustionpromoters in FCC units hasincreased in recent years due tostricter NOx emission limits andimplementation of EPA consentdecrees. Further, the recent EPAissued final amendments to itsNew Source PerformanceStandards for PetroleumRefineries indicate that additivesare now included as BestDemonstrated Technology in the

reduction of FCCU NOx emis-sions. Studies to determinemechanisms by which low NOxpromoters reduce NOx, as wellas determining the FCCU operat-ing parameters that effect NOxformation are the focus of thispaper. A lab scale regeneratortest unit was used to study thecombustion of coked ecat at con-ditions that closely simulate theregenerator of an FCCU. This

unit was used to explore theimpact of certain regeneratorvariables, including excess O2level and type of combustion pro-moter on CO and NOx emis-sions. In addition, fixed bedreactor experiments were carriedout to study the oxidation ofreduced nitrogen species on plat-inum (Pt) and non-Pt based com-bustion promoters to helpelucidate mechanistic differences.

Development of Next GenerationLow NOx Combustion PromotersBased on New Mechanistic Insights

14 ISSUE No. 107 / 2010

Based on this improved mecha-nistic understanding of how lowNOx combustion promoters work,a new combustion promoter hasbeen developed. Commercialfield trials show excellent results.

Background

FCC units account for about10% of the nitrogen oxide emis-sions generated by stationarysources in the United States.These NOx emissions are theresult of nitrogen impurities inthe feed depositing on the cata-lyst during the cracking reaction.When the coke is burned off inthe regenerator, a portion of thenitrogen is converted into NOx.Since NOx emissions are a con-tributor to acid rain, precursors inthe formation of ground levelozone, and contribute to respirato-ry health impacts, the EPA andvarious state and local agencieshave been tightening NOx emis-sion standards over the lastdecade1,2.

A variety of NOx reductionoptions, both catalytic and hard-ware oriented, are available torefiners to comply with limits onNOx content emitted from theFCCU regenerator flue gasstream. One of the best meth-ods of meeting these regulationsis the use of low NOx combus-tion promoters. This methodhas the advantage of beingsimple and inexpensive since itreplaces traditional Pt-basedpromoter, and also typicallyrequires no additional infrastruc-ture or chemical reactants. Inaddition, the U.S. EnvironmentalProtection Agency concludedthat newly adopted emissionlimits utilizing additives andcombustion controls wereachievable, cost effective andhad fewer secondary impacts

than more costly hardware ori-ented control technologies3.

The U. S. EPA issued finalamendments to its New SourcePerformance Standards forPetroleum Refineries (NSPS)3

on June 24, 2008. Within thisamendment, the EPA states thatthe currently Best DemonstratedTechnology (BDT) to NOx emis-sion control now includes theuse of additives in conjunctionwith an upwardly revised NOxemission limit of 80 ppmv basedon a 7-day rolling average.Typically, under EPA ConsentDecree proceedings, FCCUoperations have been restrictedto a NOx emission limit of 20ppmv based on a 365-day rollingaverage and 40 ppmv based ona 7-day rolling average. ThisNSPS amendment now also rec-ognizes the secondary environ-mental impact that many of thehardware solutions inflict uponthe environment, inherent intheir operation to achieve a 20ppmv maximum NOx emissionlimit. These secondary impactsinclude PM (Particulate Matter)as well as additional SO2 andNOx emissions resulting fromincreased electrical demand. Inaddition, many of the hardwaresolutions require supplementarychemical reactants that add haz-ards and emission problems oftheir own1. As such, non-plat-inum formulated oxidation pro-moters and advanced oxidationcontrols typically are anticipatedto provide the least overall envi-ronmental impact, as they gen-erally do not generate furthersecondary environmental emis-sions.

Even though there are manyadvantages for the use of lowNOx promoters, there are somelimitations, especially with first

generation promoters. Theseinclude variable and at times lim-ited NOx reduction and alsooccasionally low CO combustionactivity. The variability is thoughtto be due to the wide range ofunit FCCU operating conditions,as well as the variety of regener-ator configurations. The pur-pose of this paper and the R&Dwork at Grace is to understandthe reactions behind NOx forma-tion and destruction so improvedadditives can be developed thatare more effective and less vari-able in their performance. Inaddition, work is on-going tounderstand the operating condi-tions that affect NOx formation inorder to develop recommenda-tions to help refiners optimizetheir unit to minimize NOx.

NOx Emission Mechanism

NOx in the FCC regeneratororiginates from feed nitrogenbeing deposited on the catalystas coke. When the nitrogencontaining coke is burned off inthe regenerator, about 10% ofthe nitrogen is emitted as NOxand the remainder is emitted asnitrogen. Thermal NOx, whichresults from the oxidation ofmolecular nitrogen (N2), is not asignificant source of NOx at FCCregenerator temperatures. Thishas been shown to be the caseboth by thermodynamic calcula-tions and experimentally by per-forming a nitrogen mass balancearound an FCC pilot plant unit4,5.During the combustion of coke,data indicates that the nitrogenin the coke is first released as N2

or as a reduced nitrogen com-pound, such as HCN. In thepresence of water vapor, gener-ated by the combustion of coke,the HCN is hydrolyzed to NH36,7.These reduced nitrogen speciesare then further oxidized to

GRACE DAVISON CATALAGRAM 15

CokeNitrogen

Reduced Nitrogen Species(NH3, HCN)

NOx + Reductant

Nitrogen

(2B)

(2A)

(1)

Figure 1Major NOx Reduction Pathways

either N2 or NOx. The NOx isalmost exclusively in the form ofNO. Once the NOx is formed itcan also react with variousreductants, such as carbon orCO to form nitrogen.

In full burn units, traditional Pt-based combustion promoters arevery effective at reducing CO butalso dramatically increase NOxemissions. Low NOx combus-tion promoters were introducedto solve this problem by retain-ing the CO oxidation function buteliminating the sharp increase inNOx. The low NOx combustionpromoters typically contain non-Pt noble metals, potentially othertransition metals, and have mod-ified alumina supports that helpwith the NOx reduction func-tion8,9,10.

Based on the reaction pathwayillustrated in Figure 1 for the for-mation and destruction of NOx,there are two major pathways bywhich low NOx combustion pro-moters can lower NOx. The first(1) is catalyzing the reduction of

NOx to nitrogen. The second (2)is acting on the NOx precursorand minimizing its conversion toNOx. This would be accom-plished by promoting the oxida-tion of the reduced nitrogenspecies to nitrogen (eqn. 2A)rather than to NOx (eqn. 2B).

Equation 2A

4NH3 + 3O2 = 2N2 + 6H2O

Equation 2B

4NH3 + 5O2 = 4NO + 6H2O

The first mechanism (1) hasbeen shown to be facilitated byGrace combustion promoters.This work is outlined in twopapers Grace published jointlywith researchers at theUniversity of South Carolina11,12.The data indicated that additivespromoted the reduction of NO byCO through an isocyanate inter-mediate stabilized by the surfaceof the low NOx combustion pro-moter. The second mechanism(2), involving the oxidation ofreduced nitrogen species toNOx, is the subject of work inthis paper. The research eluci-dating these mechanisms andthe development of new Gracelow NOx combustion promoterswas carried out in a fluidizedbed Regenerator Test Unit aswell as in a fixed bed reactor, asdescribed below.

Experimental

Regenerator Test Unit

A laboratory scale RegeneratorTest Unit (RTU) was utilized totest the performance of low NOxcombustion promoters and con-ditions that affect NOx emissionsin the FCC regenerator13. TheRTU simulates an FCC regener-

ator by feeding coked catalystonto the top of a fluidized bedwhere the coke is burned offunder controlled conditions.Catalyst is also constantlyremoved, generating an equili-brated catalyst ranging fromcompletely coked to completelyregenerated catalyst in the reac-tor. This closely replicates anactual FCC regenerator environ-ment where additive perform-ance can be determined andwhere regenerator conditionscan be systematically changedto determine their effect on NOxemissions.

The additives were tested after ametals-free Cyclic PropyleneSteam (CPS) deactivation. Thecommercial FCC catalyst used inthe study was steam deactivatedfor 4 hours at 1500ºF in 100%steam. After deactivation, it wascoked in Davison Circular Riserpilot plant using an FCC feedthat contained 0.18 wt.% totalnitrogen, 0.42 wt.% sulfur, and5.1 wt.% Conradson carbon.The coked catalyst containedapproximately 1 wt.% coke. Fortesting purposes, the deactivat-ed additive was blended with thecoked catalyst at a 0.2 wt.%level. During testing the reactortemperature was maintained at700ºC, and the excess oxygenwas controlled at 1.1%. Datawere collected for 60 to 90 minafter the steady state wasachieved.

Fixed Bed Reactor

Fixed bed reactor work was car-ried out, in collaboration withUniversity of South Carolina14, tocompare the oxidation of thereduced nitrogen species over avariety of noble metals on a lowNOx combustion promoter basesupport. Ammonia was used asthe model compound due to its

availability, relatively low toxicityand belief that it is a major inter-mediate species in the formationof NOx. The metals weredeposited on the support usingsoluble metal salts and impreg-nating to incipient wetness. Thecatalysts were dried and thencalcined. The oxidation ofammonia in the presence of oxy-gen was carried out at 700ºC tosimulate a typical FCC regenera-tor temperature. For eachexperiment 0.2 grams of additivewas blended with 3 grams ofquartz in the fixed bed. Prior toanalysis, the samples were treat-ed in a 10% O2/He flow at700ºC. The ammonia feed gasconcentration used for the reac-tion was 500 ppm. The testingwas carried out using oxygenlevels of 500 ppm and 2000ppm. The data were collectedunder steady-state conditions atconstant gas hourly space veloc-ity (GHSV) of 30 L/gm/hr. Thereaction products from the reac-tor were fed to a GC-mass spec-trometer for identification andquantification.

Results

The oxidation of ammonia toNOx and N2 was carried outover the low NOx combustionpromoter support as well as foreach of the supported metals.The low NOx combustion pro-moter support was consideredthe base line and additional con-version considered due to theeffect of the metal. The data inFigure 2, for the 2000 ppm O2case shows that the Pt-basedpromoter converts a significantlyhigher percentage of ammoniainto NOx than either noble metal#1 or #2. The noble metal #1catalyst is the most selective forconverting NH3 to N2 followed bynoble metal #2 catalyst. Theseresults indicate that the selectivi-

16 ISSUE No. 107 / 2010

40

50

60

70

0

10

20

30

Pt Metal #2 Metal #1

Noble Metals

NO

xFo

rmat

ion

(%)

Figure 2NOx Formation vs. Noble Metal Type

ty of the combustion promoter incatalyzing the oxidation ofreduced nitrogen species toeither N2 or NO is a key differ-ence between the performanceof Pt and non-Pt promoters inthe FCC regenerator. The effectof higher oxygen level on theselective oxidation of NH3 wasalso studied. The data showsthat increasing oxygen levelsfrom 500 ppmv O2 to 2000 ppmvO2, over the Pt promoter,increases the amount of ammo-nia converted to NOx by about20%. Both of these observa-tions are consistent with what isobserved in FCC regeneratorswhere Pt-based promoters andhigh excess O2 levels both tendto increase NOx emissions.

Resulting Products

CP® PGrace Davison’s third generationlow NOx combustion promoter,CP® P, has recently been intro-duced to select refiners for com-mercial scale evaluation.Preliminary results from thesetrials are confirming that theintended characteristics of thisthird generation low NOx com-bustion promoter have beenachieved.

CP® P has been designed as aplatinum free formulation, yield-ing quick response to afterburnand/or CO excursion situations,as traditionally has beenobserved with Pt formulated COpromoters. Yet, CP® P results inlower NOx emissions and veryquick NOx emission decay peri-ods. While “rescue” dosing of Ptformulated CO promoter wouldoften result in elevated and lin-gering NOx emissions for up to2-4 weeks, the NOx decay peri-od resulting from “rescue” dosingof CP® P tends to span only afew days. Further, unlike earlier

generations of low NOx promot-ers, CP® P often does notrequire strict adherence to dailymaintenance dosing. However,consistent daily dosing of CP® Premains the preferred routetowards achieving predictableafterburn, CO, and NOx emis-sion control and balance.

Below are the initially receivedtestimonial responses fromFCCU locations regarding theperformance characteristics ofCP® P.

Wyoming Refining –Newcastle, WY

“Wyoming Refining Companyhas been a user of GraceDavison’s CP® 5 combustionpromoter since we started ourFCC up in 2000. We recentlyswitched to their CP® P productand are achieving the sameresults as CP® 5. Our reasoningfor the change was to help withthe reduction of NOx in ourregenerator flue gas. So far,

with the addition of CP® P, we donot see an increase in the NOxwhenever the Promoter isadded.”

Montana Refining –Great Falls, MT

"We do see good results andhaven’t seen an increase in COwith the amounts we have beenusing."

The CP® P usage rate is about25% lower than the first genera-tion low NOx promoter. CP® P ismore active with an immediateafterburn and CO response, atsimilar NOx levels, as withXNOX®.

Gulf Coast, USA Refiner

An immediate drop of 40-50°F inregenerator cyclone tempera-tures (at constant dense bedtemperatur) was observed afterthe switch to CP® P from a com-petitive low NOX promoter.

GRACE DAVISON CATALAGRAM 17

The lower temperatures allowedfor a reduction in air rate andexcess O2 in an FCCU that is airrate limited during warmermonths. Thus providing the flex-ibility to operate with lower pre-heat and higher cat-to-oil ratiosduring warmer weather. Pre-viously, operations wouldattempt to increase air to oxidizeCO to CO2 in the bed to keepregenerator dilute phase temper-ature in check.

Additionally, CP® P, being a non-platinum formulated CO promot-er, greatly enhances the disposi-tion possibilities of a refiner’secat. CP® P is competitivelypriced to attract FCCU opera-tions in need of either a low NOxCO Promoter, or simply areplacement to an existing midactivity platinum formulated pro-moter.

Next Generation Low NOxPromoter

Grace Davison’s continuing R&Dwork on mechanistic pathwaysfor the formation and destructionof NOx in the FCC regenerator,indicate that additional improve-ments to low NOx promoters arestill possible. Research and fielddata show that there is a generalrelationship between CO andNO that makes it difficult toachieve very low CO levels with-out dramatically increasing NOx.By fine-tuning and combining theproperties of an active metal andthe appropriate support materialwe have preliminary data thatshows further reductions in NOx,at constant CO levels, areachievable. Testing data fromGrace Davison’s RTU, demon-strate these improvements inFigures 3A and 3B. The datareveals that the CO combustionactivity of this fourth generationpromoter is similar to Pt-based

CO

Com

bust

ion

Act

ivity

(%)

40

50

60

70

80

90

100

0

10

20

30

CP® P 4th Gen LNPCombustion Promoters

Figure 3aCO Combustion Activity

NO

Emis

sion

s(p

pmv) 70

75

50

55

60

65

CP® P 4th Gen LNPCombustion Promoters

Figure 3bNOx Emission Comparison

18 ISSUE No. 107 / 2010

promoters and CP® P but makeslower NOx. We expect this newtechnology will be commercial-ized in 2011.

Summary

Grace research and develop-ment efforts have led to thedevelopment of CP® P, a newlow NOx combustion promoter.Data from multiple field trials hasindicated excellent CO controlwith quick response to afterburnand/or CO excursions, like tradi-tional Pt-based promoters.However, unlike traditional pro-moters, CP® P provides lowerNOx emissions and very quickNOx emission decay periods.

This new promoter was devel-oped as an outgrowth of R&Dwork directed towards under-standing the mechanistic path-ways for NOx formation in theFCC regenerator. The reducednitrogen species generated dur-ing the burning of coke in theregenerator are the key interme-diate species in minimizing NOxformation. CP® P is much moreeffective at converting thesereduced species to N2 than Pt-based promoters, which tend toconvert them to NOx. In addi-tion, CP® P is effective at con-verting NOx that has beenformed in the regenerator backto N2 via a reaction with reduc-ing species.

Due to the success of low NOxpromoters and lack of need foradditional infrastructure or otherchemical reactants, these pro-moters are now considered bythe EPA to be the BestDemonstrated Technology forabating NOx emissions fromFCC regenerators. Grace iscontinuing work in alignmentwith this BDT conclusion by theEPA, directing continued

research and developmentefforts towards further under-standing both the NOx formationmechanisms and improved cat-alytic methods for reducing NOx.

References

1. Frank S. Roser, Mark W. Schnaith, and

Patrick D. Walker, “Integrated View to

Understanding the FCC NOx Puzzle,” UOP

LLC, Des Plaines Illinois, 2004 AIChE Annual

Meeting.

2. Cheng, Wu-Cheng; Habib, E. Thomas,

Jr; Rajagopalan, Kuppuswamy; Roberie,

Terry G.; Wormsbecher, Richard F.; Ziebarth,

Michael S., Fluid Catalytic Cracking,

Handbook of Heterogeneous Catalysis (2nd

Edition) (2008), (6) 2741-2778.

3. New Source Performance Standards

(NSPS) for Petroleum Refineries, at 40

C.F.R. Part 60, Subpart J/Ja. 73 Fed. Reg.

35838 (June 24, 2008). The amendments

were proposed in 2007 as the outcome of

the periodic review of NSPS standards

required under the Clean Air Act -- Section

111(b)(1). 72 Fed. Reg. 27278 (May 14,

2007). The rules provide technical correc-

tions to the existing Subpart J standards and

create a set of new emissions for fluid cat-

alytic cracking units (FCCU), fluid coking

units (FCU), sulfur recovery plants (SRP),

and fuel gas combustion devices for facilities

that were newly constructed, modified or

reconstructed after May 14, 2007. The new

rules became effective on June 24, 2008.

4. Xinjin Zhao, A.W. Peters, G. W.

Weatherbee, Nitrogen Chemistry and NOx

Control in a Fluid catalytic Cracking

Regenerator, Ind. Eng. Chem. Res. 1997, 36,

4535-4542.

5. K. L. Dishman, P. K. Doolin, L. D.

Tullock, NOx Emissions in Fluid catalytic

Cracking Catalyst Regeneration, Ind. Eng.

Chem. Res. 1998,37, 4631-4636.

6. G. Yaluris,, A. Peters, Additives Acieve

Ultra-Low FCCU Emissions, NPRA Paper

AM-05-21, 2005

7. J. O. Barth, A. Jentys, J. A. Lercher, On

the Nature of Nitrogen Containing

Carbonaceous Deposits on Coked Fluid

Catalytic Cracking Catalysts, Ind. Eng.

Chem. Res. 2004,43, 2368-2375.

8. A.W. Peters, J.A. Rudesill, G.D.

Weatherbee, E.F. Rakeiwicz, M.J. Barbato-

Grauso, US Patent 6,143,167 2000, to

W.R.Grace & Co.-Conn.

9. A.W. Peters, E.F. Rakeiwicz, G.D.

Weatherbee, X. Zhao, US Patent 6,165,933

2000.

10. G. Yaluris, and J.A. Rudesill, US Patent

6,881,390, 2005.

11. Oleg S. Alexeev, Sundaram

Krishnamoorthy, Cody Jensen, Michael S.

Ziebarth, George Yaluris, Terry G. Roberie,

Michael D. Amiridis , In Situ FTIR

Characterization of the Adsorption of CO and

its Reaction with NO on Pd-Based FCC Low

NOx Combustion Promoters. Catalysis

Today, Volume 127, Issues 1-4, 30

September 2007, Pages 189-198.

12. Oleg S. Alexeev, Sundaram

Krishnamoorthy, Michael S. Ziebarth, George

Yaluris, Terry G. Roberie, Michael D.

Amiridis, Characterization of Pd-Based FCC

CO/NOx Control Additives by In Situ FTIR

and Extended X-ray Absorption Fine

Structure Spectroscopies. Catalysis Today,

Volume 127, Issues 1-4, 30 September 2007,

Pages 176-188.

13. G. Yaluris, X. Zhao, and A. W. Peters, “

FCCU Regenerator Lab-Scale Simulator for

testing New Catalytic Additives for Reduction

of Emissions from The FCC Regenerator”,

Proceedings of the 212th ACS National

Meeting, Orlando, FL, Aug, 1999, 41 (3)

P.901.

14. Michael Amiridis, Oleg Alexeev, Behnam

Bahrami (Chemical Engineering, University

of South Carolina), Udayshankar Singh,

Michael Ziebarth (W.R. Grace & Co.-Conn.),

Manuscript preparation currently in progress.

GRACE DAVISON CATALAGRAM 19

20 ISSUE No. 107 / 2010

Our newest CO Promoter, CP®P delivers quick

CO/afterburn response, equivalent to traditional

Platinum formulated promoters with up to 20%

lower NOx emissions compared to competitive

products.

Commercialized in late 2009, six FCC units are

currently using CP®P and three additional trials are

planned. In commercial applications, CP®P has

• 75% lower usage rates compared to first

generation low NOx promoter

• Allowed operation at lower excess O2 in an

air-limited FCCU

• An immediate 40 – 50°F drop in hottest cyclone

temperature at constant dense bed temperature

after switch from competitor

Its copper-free formulation allows for enhanced

disposition possibilities for equilibrium catalyst and

has no special handling requirements. CP®P is

available in

• 5 lb. bags

• 30 lb. pails

• 300 lb. drums

• 2000 lb. totes

CurrentUsers

Date CP® PStarted

BasePromoter

ExpectedStart 2ndQtr 2010

Competitor 1Non-Pt Based

Promoter

CP® AExpectedStart 1stQtr 2010

XNOX®

CP® 5

ExpectedStart 1stQtr 2010

Feb ’10

Competitor 1Non-Pt Based

PromoterFeb ’10

CP® 5Feb ’10

Competitor 2Non-Pt Based

Promoter

XNOX®

CP® 5

Jan ’10

Nov ‘09

Sep ‘091

2

3

4

5

6

7

8

9

Table ICurrent and Planned CP® P Users

Grace Davison Introduces CP®P,Our Third Generation Non-PlatinumLow NOx CO Promoter

CO

Inde

xPe

rcen

t

1st Generation Low NOxCombustion PromoterCP® P

55

50

45

40

35

30Reduced Variability with CP® P

Figure 1CP® P Reduces Variability

catalysts@grace.com www.e-catalysts.comartinfo@grace.com

Catalagram®, Grace®, Grace Davison®, GENESIS®, MIDAS®, IMPACT®, GSR®, AURORA®, ADVANTA®, Super DESOX®, D-PriSM®,SuRCA®, GSR®-5, OlefinsMax®, OlefinsUltra® and SmART Catalyst System® are registered trademarks in the United States and/orother countries, of W. R. Grace & Co.-Conn.

ApART™, AT™, DX™ and StART™, SmART Catalyst System® are trademarks of Advanced Refining Technologies, LLC.ART® and ADVANCED REFINING TECHNOLOGIES® are trademarks, registered in the United States and/or other countries,of Advanced Refining Technologies, LLC.

Astera™ and Alcyon™ are trademarks of W. R. Grace & Co.-Conn.

Grace Davison® is a business unit of W. R. Grace & Co.-Conn.

This trademark list has been compiled using available published information as of the publication date of this brochure and may notaccurately reflect current trademark ownership.

© 2010 W. R. Grace & Co.-Conn.

The information presented herein is derived from our testing and experience. It is offered, free of charge, for your consideration,investigation andverification. Since operating conditions vary significantly, and since they are not under our control, we disclaim any and all warranties on the resultswhich might be obtained from the use of our products. You should make no assumption that all safety or environmental protection measures areindicated or that other measures may not be required.