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    GS-Caltex RFCC Process

    Overview

    June, 2013

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    Residue Fluidized Catalytic Cracking is a process used to convertresidues to gasolines and middle distillates

    Atmospheric Residue (100%)

    H2, C1 - C2 Gases

    LPG

    C5

    Cracking Naphtha (LCN)

    Light Cycle Oil (LCO)

    RFCC Oil (RO)

    CrackingCatalyst

    Residue Fluidized Catalytic Cracking

    Fluidizedmeans that cracking and coke burning reactions take placewith fluidized cracking catalyst

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    Introduction to RFCC

    History

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    Project Proceedings

    1992. 1 Kick-off Meeting with Stone & Webster

    1994. 2 Pile Driving for Foundation

    1994. 7 Erection of Main Fractionator

    1994. 9 Erection of Reactor & Regenerators 1995. 8 CO Boiler Firing

    1995. 9 Mechanical Completion

    1995.12 Feed-in

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    Project Outlines

    Capacity : 70,000 B/D

    Plot Area

    On Site : 70,000 M2

    Off Site : 240,000 M2

    Investment Cost : US $ 530Million

    Manpower : 1,110,000 Man-days

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    RFCC Complex Capacities and Licenses

    Unit Capacity Licensor Detail Eng Const.

    RFCC 70,000 B/D S & W LGEN DIC

    Slurry Filter 8,700 B/D PALL PALL DIC

    Sulfur Bed 17,500 B/D ISG ISG DIC

    LPG Sweetening 17,500 B/D Merichem DEC LGC

    C5 Sweetening 8,500 B/D UOP DEC LGC

    LCN Sweetening 19,500 B/D UOP DEC LGC

    HCN Sweetening 12,000 B/D UOP DEC LGC

    SRU 100 Ton/Day TPA DEC LGC

    DeSOx 566,200 NM3/Hr Haldor Topsoe DEC DIC

    MTBE 2,500 B/D CD Tech LGEN DIC

    (TAME) (2,800 B/D) (CD Tech) (LGEN) Delayed

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    Main Features of GS-Caltex RFCCU

    One of the Largest RFCC Units in the World

    Most Severe Design Feedstock (CCR: 5~ 7 wt%)

    Two Stage Stacked Regenerators

    Two Catalyst Coolers

    LD2 Separator in Reactor (2009 RSS Separator)

    Power Recovery Train

    Two CO-Boilers

    1st Application of Haldor Topsoe DeSOx Unit to RFCCU

    Oxygen Enrichment

    ZSM-5 Injection

    APC/VPS Utilization

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    RFCC Improvement

    History

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    Improved Items Since Start-up (1)

    In 1996

    Conversion Precursor Analysis of Feed Stock

    Cat. Cooler Tube Leak Solve (Published on O&GJ)

    Radio-tracer Study

    Detected 80% Vapor Underflow at the Ramshorn Separator

    TPA(Top Pump Around) Injection in Feed Nozzle

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    Improved Items Since Start-up (2)

    In 1997

    Slurry Filter Troubleshooting(Published in O&GJ)

    Ramshorn Separator Modification

    Yield Increase 3 Vol%(Dry Gas, Coke Make Decrease)

    Modified Dust Removal System of 3rd Stage Separator

    Improvement DeSOx Unit

    Catalyst Screening System

    SO2 Converter

    Stack Plume

    Mechanical(Fabric Bellows, Acid pump, etc)

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    Improved Items Since Start-up (3)

    In 1998

    Improved Fouling of MF Bottom System Through

    HP Steam Generator(152E-201A/B/C/D) Tube Size up

    Installed Additional Air Compressor

    Integrated Amine System(DGA to DEA)

    Catalyst Evaluation

    DCR Set up & Test

    High Conversion, Less Coke Make Catalyst Selection

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    Improved Items Since Start-up (4)

    In 1999

    Installed O2 Enrichment(100% O2 Injection) System

    LPG Capacity Increase Through Common LPG Unit

    Recovered Flaring LPG From Sulfur Bed

    Modified ESP Ash Handling System

    Operation optimization

    Operation Guide Set-up Through Test Run

    Dry Training For Emergency S/D Case

    Troubleshooting History Keeping & Training

    Knowledge Sharing Network Establish(Homepage)

    Recorded Max Feed of 83,700 BPSD in Dec 12, 1999

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    Improved Items Since Start-up (5)

    In 2000

    Expander Service

    Cat. Cooler Steam Let-down System Service

    Held 3rd RFCC Peer Review

    Injected ZSM-5

    R2 Partial Burning Mode Operation

    Recorded Max Feed of 84,500 BPSD on March 30, 2000 Recorded Conversion Max (77.5%)

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    Improved Items Since Start-up (6)

    In 2001

    Expander Modification 2 Stage to Single

    Modified Air Blower Filter to Dual Bag Filter System

    Increased O2 Injection Capacity by 12,000 Nm3/Hr Installed 4th Cyclone at Downstream of 3rd Stage Separator

    Installed LPG Vaporizer for RFCC

    Replaced Stripper Reboiler and Modified Column Internal Modified DeC3 Column Internal

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    Improved Items Since Start-up (7)

    In 2005

    Modified Feed Nozzle to Micro-Jet Type (ABB-Lummus)

    Introduced Selective Hydrogenation Unit (SHU)

    Replaced Main-Fractionator Tray

    Replaced Stripper Tray

    Replaced Column Trays (DeC5, DeC4, DeC3, Splitter)

    Replaced Primary & Secondary Absorber Trays

    Improved Cooling, Pumping & Hydraulic Systems of the

    Downstream Units

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    Improved Items Since Start-up (8)

    In 2009

    Reactor RSS

    Stripper Packing Install

    Cyclone Replacement

    DeSOx GGH Replace

    DeC4 Auxilary Rebolier Install

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    Improved Items Since Start-up (9)

    In 2012

    RSS Improvement

    ESP Modification

    WSA Condenser Glass Tube Modification

    SO2 Converter Burner Replace

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    RFCC Catalyst Employment

    YearCatalystBrand

    Catalyst FeatureDaily

    Usage,

    ton

    Feed Rate,BD

    Price,USD/MT

    1995

    1996

    GraceDavisonOrion I

    Start Up CatalystRecommended by Licensor (SWEC)

    26 64,000 1,900

    1996

    1997

    GraceDavisonOrion II

    Optimize Catalyst Activity 28 67,000 1,900

    1997

    2000

    BASFUltrium I

    Improve Catalyst Activity(Less Bottom)

    21 72,000 1,800

    2000

    2003

    BASFUltrium II

    Improve Bottom Cracking & ActivityRetention (Less Bottom)

    25 78,000 1,800

    2003

    2008

    BASFUltrium III

    Improve Coke Selectivity & MetalTolerance (Higher Feed & Less CatAddition)

    27 90,000 1,900

    2008 Now

    JGC C&CCVZ I

    Improve Metal Tolerance(Less Cat Addition)

    20 92,000 2,700

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    RFCC Operation &

    Monitoring

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    Key Parameters

    Feed

    Quality

    Operation

    Variables

    Catalyst

    Properties

    Converter

    (Rx-Regen)

    Catalytic

    Cracking

    R/C

    (80,000 B/D)

    Dry Gas (27,000 Nm3/Hr)

    C3 (11%)

    C4 (16%)C5 (15%)

    LCN (30%)

    HCN (7%)

    LCO (15%)

    RO (9%)

    Coke (8~9 wt%)

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    Feed Properties

    Physical Property

    API Gravity : 19~22 (API = 141.5/Sp.Gr. - 131.5 ) Distillation Temp 50% : 480~520 C

    Aniline Point : 90~100 C

    Viscosity : 150~200 cSt @ 50C

    MCR(Micro Carbon Residue) : 4.5~6 wt%

    Sulfur : 1.6 ~ 2.1 wt%

    Nitrogen : 1300~1600 ppm

    Metal (Ni:5~12 ppm/V: 5~20/Fe: 2~4), Na (

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    Catalyst Properties

    Silica(SiO2), Alumina(Al2O3) based Zeolite Catalyst

    Component : Zeolite, Matrix, Binder, Filler Physical Property

    APS(Average Particle Size) : 80 um

    ABD(Apparent Bulk Density) : 0.8~0.9 g/cc

    PV(Pore Volume) : 0.3 cc/g

    MAT(Micro Activity Test) : 68~70 wt%

    Surface Area : 140 m2/g,

    Chemical Property

    Nickel(3500 ppm), Vanadium(5000 ppm), Fe(5500 ppm)

    Carbon : 0.04~0.06 wt%

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    Operation Variables

    C/O Ratio : 6.0~7.0

    ROT : 520 ~ 530 C

    R2 Temperature : 720 ~ 730C

    PHT : 180 ~ 200C

    TPA : 0 ~ 5,000 B/D

    Cat. Make-up Rate : 20 ~ 30 Ton/Day

    Air Flow Rate : 320 ~380 KNM3/Hr

    Oxygen Flow : 0~12,000 Nm3/hr

    ZSM-5 Injection : 0.5 ~ 0.8 Ton/Day

    MF Top Temperature : 125~130C

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    Yield Pattern and Conversion

    Feed : 92,000 BPSD (ATB)

    Yield (vol% FF)

    LPG : 26.8

    C5 ~ HCN : 53.3

    LCO : 16.4

    DO : 8.3

    Total : 104.8 Conversion : 75.3 vol%

    Coke Yield : 8.1 wt%

    By-product

    Fuel Gas : 29,700 NM3/Hr Molten Sulfur : 126 Ton/Day

    H2SO4 : 80 Ton/Day

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    Profit Maximization

    Profit Feed Cost : $ 38.6/Bbl

    Product Cost : $ 59.4/Bbl Gross Margin : $ 20.8/Bbl

    Opex. Cost : $ 1.1/Bbl

    Net Margin : $ 19.7/Bbl

    What gives more Profit? Source of Crude Mix

    Exchange Rate

    Seasonal Price Change of Pr