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Hydroprocessing Catalysts from The Chevron and ... - · PDF fileEditor’s Note: Although this is only the second special issue of the Catalagram ® dedicated solely to hydroprocessing,

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  • Hydroprocessing Catalysts fromThe Chevron and Grace Joint Venture

    106 SPECIAL EDITION Fal l 2009

  • Editors Note:

    Although this is only the second special issue of the Catalagram dedicated

    solely to hydroprocessing, we at Advanced Refining Technologies salute our sis-

    ter publication, the Grace Davison Catalagram on the fiftieth anniversary of its

    publication.

    Advanced Refining Technologies has reaped the benefits of Grace Davisons

    long-standing technical leadership in refining catalyst manufacture and technical

    service and strengthened it with the technology power of Chevron R&D and

    process expertise.

    As a result, ART has lept to a leadership position in hydroprocessing catalysis

    since it was formed eight years ago. We offer a full range of HPC catalysts for

    distillate and fixed bed resid hydrotreating and ebullating bed resid hydrocrack-

    ing and are recognized as the industry leader in resid hydroprocessing technol-

    ogy. Our technical service group, backed by both Chevron and Grace R&D, is

    able to solve your most difficult processing issues.

    We hope you find the information provided here helpful in your operations. Like

    the Grace Davison Catalagram, we look forward to celebrating the 50th anniver-

    sary of Advanced Refining Technologies leadership.

    Sincerely,

    Scott K. PurnellGeneral Manager and Managing DirectorAdvanced Refining Technologies

  • In this Special Issue of the CATALAGRAM

    The SmART Catalyst System: Meeting the Challenges of Ultra Low Sulfur DieselBy Charles Olsen, Ph.D.In this reprint from Catalagram 97 from 2005, we update commercial usage of theSmART Catalyst system, which utilizes both CoMo and NiMo catalysts, staged in theproper proportions to provide the best performance while at the same time meetingindividual refiner requirements. The catalyst staging is designed to take advantage ofthe different reaction mechanisms for sulfur removal. The article features an update oncurrent ULSD operations with the SmART Catalyst System Series.

    Continued Improvements in Advanced Pretreating by ART With Our NewestFCC Pretreat Catalyst, AT795By Brian WatkinsAs challenges in meeting clean fuels regulations continue to become more daunting,Advanced Refining Technologies continues to improve its line of ultra high activity FCCpretreat catalysts for our ApARTTM Catalyst Systems. This article is an overview of theperformance of the newest member of our FCC pretreat family, AT795, which is capa-ble of significantly reducing required SOR temperatures for both HDS and HDN.

    Cetane Improvement In Diesel Hydrotreatingby Greg Rosinski and Charles Olsen, Ph.D.This article discusses the importance of cetane in ULSD. The SmART Catalyst System,which utilizes both the CoMo and NiMo catalyst, results in a cetane uplift which is near-ly two numbers higher than an all-CoMo system with only a small increase in hydrogenconsumption. For H2 constrained refiners this is an ideal solution for improving theproduct cetane.

    Hydrocracker Pretreat Catalyst DevelopmentBy Dave Krenzke, Ph.D, Jifei Jia, Ph.D., Charles Olsen, Ph.D, Brian Watkinsand Woody Shiflett, Ph.D.ART introduces the second generation DX catalyst for hydrocracker pretreat, 590DX,our new high performance technology aimed at helping refiners meet the challengespresented by clean fuels.

    ARTs Latest Catalyst Technology for EB Resid HydrocrackingBy Balbir Lakhanpal, Darryl Klein, Pak Leung, Nan Chen, Pietro Grecoand Ashok MonteiroThe ebullating bed resid hydrocracking process has an advantage in that a wide varietyof crudes can be processed, allowing the upgrading of resid to almost saleable distil-lates, very good quality FCC/HC feed VGO, and low sulfur fuel oil. However, processingsuch opportunity crudes has its challenges, and ART has developed and commercial-ized its latest EB resid hydrocracking catalyst technology, HSLSTM, to help achieve thatgoal successfully and economically.

    Advanced Refining Technologies Answers to 2009 NPRA Q&A Questionson HydroprocessingBy Charles Olsen, Ph.D., Brian Watkins, Gordon Chu, Woody Shiflett, Ph.D.,Dave Krenzke, Ph.D., and Geri DAngelo

    2

    CATALAGRAM 106SPECIAL EDITION

    Managing Editors:Charles Olsen

    andLauren Blanchard

    Contributors:Nan ChenGordon ChuGeri DAngeloPietro GrecoJifei Jia

    Daryl KleinDave Krenzke

    Balbir LakhanpalPak Leung

    Ashok MonteiroCharles OlsenGreg RosinskiWoody ShiflettBrian Watkins

    Please addressyour comments to

    [email protected]

    2009W. R. Grace & Co.-Conn.

    The information presented herein is derived from our testing and experience. It is offered, free of charge, for your con-sideration, investigation and verification. Since operating conditions vary significantly, and since they are not under ourcontrol, we disclaim any and all warranties on the results which might be obtained from the use of our products. Youshould make no assumption that all safety or environmental protection measures are indicated or that other measuresmay not be required.

    Hydroprocessing Catalysts fromThe Chevron and Grace Joint Venture

    106 SPECIAL EDITION Fal l 2009

    Advanced RefiningTechnologies

    7500 Grace DriveColumbia, MD 21044

    410.531.4000

    www.e-catalysts.com

    10

    12

    17

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    rev.11/09

    ARTCatalagram 106 Special Edition Fall 2009 1

  • www.e-catalysts.com2

    n 2001, ART introduced theSmART Catalyst System Seriesto help refiners deal with the

    severe demands of ultra low sulfurdiesel (ULSD). The SmART Systemutilizes state-of-the-art catalyst tech-nology which is staged in the properproportions to provide the best per-formance while at the same timemeeting individual refiner require-ments. The catalyst staging isdesigned to take advantage of the dif-ferent reaction mechanisms for sulfurremoval; ART CDX, a high activityCoMo catalyst, efficiently removes theunhindered, easy sulfur via the directabstraction route and ART CDY, a highactivity NiMo catalyst, then attacks theremaining sterically hindered, hardsulfur. Pilot plant work has proven thatthe properly configured SmARTSystem provides higher activity thaneither the CoMo or NiMo catalystalone.

    The SmART Catalyst System:Meeting the Challenges ofUltra Low Sulfur Diesel

    Charles OlsenWorldwide Technical ServicesManager

    ADVANCED REFININGTECHNOLOGIESChicago, IL USA

    I ART CDX and ART CDY, individual-ly or as part of a SmART CatalystSystem, were selected for 14 dieselunits in 2004, and most of theseapplications aim to evaluate ULSDcapability and/or produce ultra lowsulfur fuels in advance of the regu-lations for economic benefit.

    Optimizing the SmART CatalystSystem

    An important aspect of the SmARTCatalyst System is determination ofthe optimum proportions of theCoMo and NiMo catalysts that willdeliver the best performance. Thisis dependent upon a number of fac-tors, including the refiners require-ments, and selected feed proper-ties and operating conditions asdiscussed in detail previously inCatalagram No. 95 (March 2004).

  • ARTCatalagram 106 Special Edition Fall 2009 3

    One clearly important parameterwhich must be considered is theboiling range of the feedstock.Sulfur speciation on a wide varietyof feedstocks has shown that thereis a strong correlation between thefraction of multi-substituted diben-zothiophenes (hard sulfur) and thefeed endpoint. Once the D86 end-point increases beyond about625F there is a rapid increase inthe fraction of hard sulfur containedin the feed. This has a large impacton catalyst activity as shown inFigure 1. The figure shows pilotplant data comparing results fromtreating two feeds with differentendpoints over the same catalystunder identical conditions. At ultralow sulfur levels there is about 30Fdifference in reactivity of the twofeeds with the lower endpoint feedmore reactive. Clearly, feed end-point and the amount of hard sulfurare critical parameters that influ-ence the optimum SmART configu-ration.

    Another critical feed property thatmust be accounted for is the nitro-gen content. It is generally accept-ed that nitrogen inhibits aromaticsaturation reactions through poison-ing of acidic sites on the catalyst.Recall that the primary reactionpathway for removal of hard sulfur isvia hydrogenation of an aromaticring, and it is not surprising thatfeed nitrogen content has a serious,negative impact on HDS activity.

    The magnitude of the impact can beseen in Figure 2 which summarizesdata for a NiMo and a CoMo catalystactivity on an SR feed before and afterselectively removing the nitrogen viaan adsorption process. The differ-ence in activity on the two feeds isquite large. Increasing the nitrogencontent from 25 to 160 ppm results ina loss in HDS activity of 40-50F forboth catalysts. Comparing the cata-lysts on the low nitrogen feed showsthat the NiMo catalyst has about 15Fhigher activity relative to the CoMocatalyst, and that decreases to anadvantage of about 5F or less on thehigher nitrogen feed. This suggeststhe impact of nitrogen is different forNiMo and CoMo catalysts with theCoMo catalyst more tolerant of nitro-

    gen. This is another important con-sideration when designing the opti-mum SmART System.

    Hydrogen availability, in terms ofhydrogen pressure and hydrogencirculation, also takes on greaterimportance in ULSD. Figure 3 is achart showing how the relative HDSrate constant changes as a functionof the excess hydrogen (H2/Oil ratiodivided by the hydrogen consump-tion) for both high and low pressureoperation. Note the range in operat-ing pressure from low to high repre-sents the conditions typicallyencountered in diesel hydrotreating.At high pressure, increasing theH2/Oil is beneficial for both SR and20% LCO feeds up to a point, af