LC- Finer, SLOVNAFT

45 th International Petroleum ConferenceJune, 2011 BRATISLAVASLOVNAFT LCF Operation experienceRobert ŽAJDLÍK, Ján GAZDÍK

LC- Finer, SLOVNAFT – general dataLicense ABB LUMMUS GLOBAL Inc. USA July 1995Fluor Daniel & Mitsubishi Heavy Ind. June 1996Start of construction June 1997End of construction September 1999Start-up on Vacuum Residue March 8th 2000Performance testAugust 24th-27th,2000

LC-Finer unit – Main objectivesVR Conversion565 degC+Reactor Temperature 416 °CReactor Pressure 18 MPaConversion 62% (design 65%)Desufurisation VR (0.95 – 1.2 wt%)Denitrification VGO (3300 – 4000 wtppm)Demetalisation VGO, VR (0.1 wtppm; 100 wtppm)MCRT Reduction VGO, VR (0.4 wt%; 22 wt%)Other ...

LC- Finer, SLOVNAFT – feed, products & yieldsFeed – Vacuum residue 155 t/hrDiluent LCO 15 t/hrDiluent MCB 10 t/hrMake-up Hydrogen 22 kg/tFeed %Vacuum Residue 86MCB 8LCO 6Total 100.0Product %Gases 4Naphtha fraction 6Diesel fraction 24VGO 28Vacuum Residue 38Total 100.0

LC- Fining familyBuild Company VR [t/hr] Bottom product2010 GS Caltex 400 Stable FO2013 Northwest Upgrading 193 IGCC2010 Shell Canada 291 Stable HSSC2007 Neste Oil 267 Fuel Oil2003 Shell Canada 527 Stable HSSC2000 Slovnaft 155 Stable LSFO1998 AGIP Petroli 167 Stable LSFO1988 Syncrude Canada 267 Coker Feed1984 BP-Amoco 500 Coker Feed+ 7 H-Oil technologies worldwide, (e.g. PKN Plock)

Importance of LC Fining for the companyNet Cash Margin ranking of the European refineries, 2008, Wood Mackenzie20Bratislava; 17.3915Duna; 12.21NCM in USD/bbl105Rijeka; 5.92Sisak; 4.42IES Mantova; 2.890-5

SLOVNAFT´s technological change over last decadeProduction (in kilotonnes) 1998 2007 changeMotor petrol 909 1 617 78%Motor diesel 1 863 2 864 54%Heavy fuel oil 1 065 207 -81%Bitumen 228 36 -84%Petrochemical and plastics 249 588 136%Other products 605 1 659 174%Total 4 919 6 536 33%Slovnaft now produces more valuable light productsother 12%other 25%bitumen 5%bitumen 1%fuel oil 22%fuel oil 3%petchem 9%petchem 5%diesel 44%diesel 38% over USD 650 mn investments spent on change ofproduct slate and fuels´ desulphurization light products > 85% of total production all motor fuels can be produced with 10 ppm qualitypetrol 18%1998before upgradepetrol 25%2007after upgrade

LC Finer - part of the complex EFPAPreparation: 1992-1996Building: 1997-2000GasesGasesVacuumResidGasesLCFVGORefineryLNHNMDVGOHDSVGOLNHNMDVGOResid.FCCMEROX LPGMEROX GASMDC 4Resid.RefineryGasesNaturalGasHPETBEALKC 4 from SCSHGasoline

Flow Diagram ... LC-Finer unit

100%Capacity utilisationLCF unit utilisation over decadeRelative on stram factorRelative on stram factor, Capacity utilisation[%]90%80%70%60%50%40%30%20%10%0%2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010Year

VRVGOGas OilKeroseneH Naphtha100.00%90.00%80.00%70.00%60.00%50.00%40.00%30.00%20.00%10.00%0.00%Yields(product rate/total liquid feed rate]L Naphthayield on feed [kg/kg]01.01.0701.02.0701.03.0701.04.0701.05.0701.06.0701.07.0701.08.0701.09.0701.10.0701.11.0701.12.0701.01.0801.02.0801.03.0801.04.0801.05.0801.06.0801.07.0801.08.0801.09.0801.10.0801.11.0801.12.0801.01.0901.02.0901.03.0901.04.0901.05.0901.06.0901.07.0901.08.0901.09.0901.10.0901.11.0901.12.0901.01.1001.02.1001.03.1001.04.1001.05.1001.06.1001.07.1001.08.1001.09.1001.10.1001.11.1001.12.1001.01.1101.02.1101.03.1101.04.1101.05.1101.06.11

80706050403020100Raw 565°C+ conversionNet conv. Raw conv.565C- in VTB 565C- in VR10.08.1026.02.1114.09.1122.01.1018.12.0806.07.0901.06.0814.11.0728.04.0710.10.06Conversion / 565C- in VTB[wt%]

35.030.025.0565°Crecovery VTB [%w]20.03.532.521.510.50Sulfur in heavy productsS in VGO S in VTb S in VR 565C- in VTB15.010.05.00.014.11.0701.06.0818.12.0806.07.0922.01.1010.08.1026.02.1114.09.1101.04.1228.04.0710.10.06Slufur content [%wt]

1000090008000Nitrogen content [wtppm]7000600050004000300020001000001.04.1214.09.1110.90.80.70.60.50.40.30.20.10Nitrogen in heavy productsN in VTb N in VR N in VGO14.11.0701.06.0818.12.0806.07.0922.01.1010.08.1026.02.1128.04.0710.10.06Nitrogen content [%wt]

Problematic issues• Feed quality changes– Sulfur and Nitrogen content– Density– MCRT– Metal content• Fouling of key equipments– LP/HT separator and downstream HEX (E101)– Atmospheric tower– Vacuum column heater–Vacuum column– HEX train• Mechanical issues (will not be discussed)

10.90.8Nitrogen [wt%]0.70.60.50.40.326.02.1114.09.1101.04.1210.08.103.43.232.82.62.42.22Nitrogen and Sulfur in VR feedSulfur Nitrogen18.12.0806.07.0922.01.1001.06.0814.11.0728.04.0710.10.06Sulfur [wt%]

Density and 10% BP of VR-feedFeed densityFeed 10% BP103056010251020520Feed density [kg/m3]101510101005480Feed 10% BP [°C]100044099599040010.10.06 28.04.07 14.11.07 01.06.08 18.12.08 06.07.09 22.01.10 10.08.10 26.02.11 14.09.11 01.04.12

MCRT Recovered at 565°70605040302010001.04.1214.09.1126.02.1110.08.102221201918171615MCRT in VR-feed06.07.0922.01.1018.12.0801.06.0814.11.0728.04.0710.10.06MCRT [wt%]Recovered 565°C

300250200150100500Metals in VR feedV Ni14.09.1101.04.1226.02.1110.08.1006.07.0922.01.1018.12.0801.06.0814.11.0728.04.0710.10.06metals content [mg/kg]

CAR7 day average CAR01.04.1214.09.1126.02.111.210.80.60.40.20Catalyst addition rateCAR on VR+MCB01.06.0818.12.0806.07.0922.01.1010.08.1014.11.0728.04.0710.10.06CAR [kg/ton]

InvitationSustainable development and HSE Aspects of Refinery and PetrochemicalOperationsMiestnosť: Hall BJune 13, 2011 (Monday), 16:20PROCESS OF WASTE CATALYSTRECOVERY FROM RESIDUEHYDROCRACKERPOLC, R.*; VDOVJAK, L.; DIKÁCZOVÁ, Z.

FoulingCritical Fouling Locations22

Fouling• Limitations• Unit is stopped every 6 – 11 months, sometimes VT bypass neededShutdown duration – from 5 to 14 days• Main reasons for S/D:• Vacuum heater limits reached - either pressure in the passes or skintemperature in convent section• VTB pumps suction loss• 11E101 H2 preheat high delta p• Roughly at about 40 tones of coke removed from equipments• Vacuum bottom exchangers cleaning frequency:• 11E302A/B - once per month• 11E308 – LP steam generator – once per 5 weeks• 11E309 – once per 6 weeks23

• Modifications done• Atmospheric bottoms (ATB) circuit installed• Main goal to remove coke from the ATB• ATB increased suction• VTB increased suction• 11E308 increased tube ID• 11E101 modification – increased tube ID and construction materialchanged, wash oil (HCO)• Introduction of new low sediment catalyst• Wash oil withdrawal downstream the exchangers• Antifouling chemicals dozing• Excessive test dome with several chemicals suppliers• Vacuum furnace operation strategy• Steam flow• Decreased outlet temperature to 376°C• Considering installation of spiral exchangers24

VTBLP/HTV103E309AE309BATMC201VACC301E308C201C301Wash-oilP305E302AE302BH301VACHeaterH301C301bottomP304

Atmospheric tower bottom400320350290300260Temperature [°C]25020015010050230200170140110Total feed [t/h]00 20 40 60 80 100 120 140Operating days80

LC Finer, SLOVNAFT

Thank you for your attention

treat gas puritymake-up H2/feed300250200150100100.0099.0098.0097.0096.0095.0094.0093.0092.0091.0090.00Other achievementsHydrogen partial pressure50001.04.1214.09.1126.02.1101.06.0818.12.0806.07.0922.01.1010.08.1014.11.0728.04.0710.10.06hydrogen purity [%vol]H2 make-up/feed rate [Nm3/m3]

200000180000160000140000120000100000800006000040000200000Feed ratesVR+LCO+MCB VR LCO MCB25%20%15%10%5%0%26.02.1114.09.1101.04.1210.08.1006.07.0922.01.1018.12.0801.06.0814.11.0728.04.0710.10.06Total Feed and VR rates [kg/hr]LCO/total feed and MCB/total feedfraction

1030VTB density and viskosity and VR-densityVTB density VR feed density VTB viskosity120010101000990800VTB density [kg/m3]970600VTB viskosity [mPa.s]950400930200910010.10.06 28.04.07 14.11.07 01.06.08 18.12.08 06.07.09 22.01.10 10.08.10 26.02.11 14.09.11 01.04.12

100%95%90%85%80%75%70%65%60%55%50%Sulfur removal efficiencyNormalised conversion (410°C, 170 t/hr)Conversion normalised conv.26.02.1114.09.1101.04.1218.12.0806.07.0922.01.1010.08.1001.06.0814.11.0728.04.0710.10.06S Conversion [%w]

HDNNormalised conversion (410°C, 170 t/hr)Conversionnormalised conv.50%45%40%35%N Conversion [%wt]30%25%20%15%10%5%0%10.10.06 28.04.07 14.11.07 01.06.08 18.12.08 06.07.09 22.01.10 10.08.10 26.02.11 14.09.11 01.04.12

120%100%80%60%40%20%0%-20%HDV removal efficiencyconversion V est. on cat k02.0E+091.8E+091.6E+091.4E+091.2E+091.0E+098.0E+086.0E+084.0E+082.0E+08.0.0E+00..........V conversion and estimated V on catalyst(bfc) [%w]k0 activity factor

HDNi removal efficiency100%conversion V est. on cat k02.0E+091.8E+09Ni conversion and estimated Ni on catalyst(bfc) [%w]80%1.6E+091.4E+0960%1.2E+0940%1.0E+098.0E+0820%6.0E+084.0E+080%10.10.06 28.04.07 14.11.07 01.06.08 18.12.08 06.07.09 22.01.10 10.08.10 26.02.11 14.09.11 01.04.122.0E+08k0 activity factor-20%0.0E+00

222120MCRT in Feed [wt%]191817161501.04.1214.09.1110.90.80.70.60.50.40.30.20.10Sediment - SHFTSediment in ATB Sediment in VTB MCRT01.06.0818.12.0806.07.0922.01.1010.08.1026.02.1114.11.0728.04.0710.10.06Sediment [%wt]

0.40.3TI Feed [%wt]0.20.110.90.80.70.60.50.40.300.2-0.10.1-0.20-0.3Sediment - SHFT-0.4-0.5-0.601.04.12Sediment in ATB Sediment in VTB TOLUENE Insoluble14.11.0701.06.0818.12.0806.07.0922.01.1010.08.1026.02.1114.09.1128.04.0710.10.06Sediments [%w]

Location of SKIN temperaturemeasurement points for foulingcontrol of BRHCK key equipment.TI3394ATMC201VACHeaterH301TI3305TI3307TI3314TI3372VACC301TI3398TI3396TI3312TI3311TI3395VTBP205TI3319TI3333P304TI3374TI3397

LC – Finer overall on-stream performanceYear VR Processed On-streamthr2000 825 553 6 9082001 967 311 7 1842002 1 040 494 7 5642003 968 176 7141 TA year2004 1 117 052 82492005 1 069 669 81402006 934 433 7162 TA year2007 1 154 919 84562008 1 147 157 84882009 1 028 163 73992010 1 020 733 7342 TA yeartotal 9 480 796

Feed deterioration impact on RX exothermsReactor exothermsR101 R102 R103 cummulative dT H2 Make-up18035016030014012010080604025020015010020500010.10.0628.04.0714.11.0701.06.0818.12.0806.07.0922.01.1010.08.1026.02.1114.09.11Exotherm [°C]Hydrogen make-up rate [Nm3/m3 feed]