1. Fluid Catalytic Cracking A.Meenakshisundaram Chennai Petroleum Corporation Limited

3. Worldwide Petroleum Product Distribution

4. OIL USE – SECTOR WISE ( million tons oil equivalent ) 4300 54 3600 52 3200 50 2800 42 Total Share of Transport 250215192140Other 1430126512161340Heating and Industrial 300250192140Petrochemical 2320187016001180Transportation 2010200019951985

5. WORLD CRUDE OIL QUALITY

9. Petroleum Refining Crude as obtained can not be used as fuel products as it is a complex mixture of various light and heavy hydrocarbons Refining involves separation of light fractions by distillation to produce distillate fuels. Heavier fractions are converted into useful fuel products by secondary processing such as FCC,Hydrocracking etc.. Environmental and Engine requirements require further transformations to make improved quality fuel products (e.g Reforming, Hydrotreating etc.)

10. Catalytic Processes in Refining Processes for Secondary Conversion - converting heavier fractions into lighter products - FCC, Hydrocracking etc.. Processes for meeting fuel engine requirements - Catalytic Reforming, Alkylation, Catalytic Dewaxing etc.. Processes for meeting Environmental requirements of fuels - HDS, Oxygenates Production, Benzene /Aromatics reduction etc. Processes for Production of Lubes - Catalytic Dewaxing, Catalytic Iso Dewaxing, Hydrocracking, Hydrofinishing etc.. Apart from the above, catalytic processes are also used in refineries for Hydrogen Production, Petrochemical Feedstocks and Speciality Products etc..

11. World Catalyst Market Sales in Billion US $ Catalyst use by Industry 1997199920012007 Environmental1.632.612.884.05 Refining2.072.172.322.84 Polymers1.702.062.222.97 Petrochemicals, Fine Chemicals 2.002.163.173.64 Total7.409.010.5913.51

12. Refining Catalyst Market FCC 40% HYDROPROCESSING 25% REF.,ISOMERIATION 15% ALKYLATION 15% OTHERS 5%

13. Petroleum Refining - Effect of Catalysis Innovations

14. FLUID CATALYTIC CRACKING

15. Fluid Catalytic Cracking Refinery process that “cracks”high molecular weight hydrocarbons to lower molecular weight. Refinery process that provides ~50 % of all transportation fuels indirectly. Provides ~35 % of total gasoline pool directly from FCC produced naphtha. ~80 % of the sulfur in gasolines comes from the FCC naphtha.

16. FLUID CATALYTIC CRACKING MAJOR SECONDARY REFINING PROCESS CONVERSION OF HEAVY FRACTIONS ( VGO -370 C+)INTO LIGHTER FUEL PRODUCTS(LPG,GASOLINE,DIESEL) CIRCULATING FLUID BED REACTOR SYSTEM (REACTOR- REGENERATOR CONFIGURATION ) MULTI COMPONENT CATALYST SYSTEM CATALYST TAILORED FOR EACH UNIT BASED ON UNIT OBJECTIVES AND CONSTRAINTS FCC IS THE WORKHORSE FOR REFINERY - MOST PROFITABLE TOO!

17. FLUID CATALYTIC CRACKING

18. Main Reactions in FCC Cracking of Paraffins,Naphthenes and side chain of aromatics Isomerisation of olefins Dehydrogenation of Naphthenes and Olefins Hydrogen Transfer Cyclization and condensation of olefins Alkylation and dealkylation

23. FLUID CATALYTIC CRACKING CATALYSTS

31. INDIAN GASOLINE SPECIFICATIONS S.No.Characterstics UnitBharat Stage II Euro III Euro IV 1Density @15 C kg/m 3 710-770 720 - 775 720 - 775 2 2Distillation Recovery upto 180 C Min.Vol% 90 75 75 3RON min 88 91 91 4Sulfur Total Max.%Mass 0.05 0.015 0.005 5Benzene Content Max %Vol 3.0(Metro) 1.0 1.0 6Olefins max. %vol 21 18 7 Aromatics Max. %vol 42 35 8RVP Max kPa 35-60 60 60

32. ADDITIVES IN FCC UNIT

33. FCC ADDITIVES ZSM-5 Additive for boosting octane number and light olefins yields (C3/C4) Alumina micro Spheres with dispersed Pt for enhancing CO oxidation in Regenerator dense bed (CO Promoter) Bottoms Cracking Additive – Alumina Matrix with tailored pores and acidity for cracking heavier fractions of the feed. Gasoline sulfur reduction additive SOx Reduction Additive for reducing SOx emissions Metal Passivators – Sb/Bi liquid compounds for Ni Passivation, Vanadium Trap for V passivation

35. ZSM-5 Additive ZSM-5 Additive - Reactant shape selectivity is in play whereby molecules are sterically discriminated based on their ability to enter the pores of the zeolite for cracking Intermediate pore size of ZSM-5 restrict the access of highly branched and cyclic hydrocarbons to the interior of the zeolite for cracking. Thus Higher Octane molecules are retained in the gasoline range Only lower octane normal and monomethyl aliphatics enter the pores and preferentially cracked to lighter products Increases the iso/normal paraffin and olefin ratio Results in higher RON, higher Propylene/Butylene yields, lower Gasoline yield About 2 to 5% dosage of additive is used with ZSM-5 crystal content of 25 – 40wt%

36. Bottom Cracking Additive Bottom Cracking Additive (BCA) in general facilitates cracking of heavy ends of the feed into intermediate range molecules suitable for further cracking by the host catalyst. Use of BCA in some units is preferred to high activity matrix especially units with coke burning limitation

42. Options for Gasoline Sulfur Removal Pretreatment of FCC Feed Treatment of FCC Naphtha Undercutting FCC Gasoline FCC Gasoline Sulfur Additive

50. Catalyst for Sulfur Reduction in Gasoline

52. CO Promoter Promotes combustion of CO to CO2(200 ppm of CO in flue gas for a 50 000 bpd FCC unit or 1.5 – 2.0 tpd) Eliminates the need for CO boiler and improves the environment by reducing CO in flue gas. Lower Carbon on Regenerated Catalyst will increase activity and better coke-conversion selectivity. Pt at 1 PPM level in the unit will promote CO oxidation. Normally a separate additive containing 500 –1000 ppmw Pt on Gamma Alumina is used. Pt catalysed CO combustion occurs readily in the dense phase at temp. 650 – 700 C

53. Refinery CO Control C + O2 = CO2  H = -94 Kcal/mole C +1/2 O2 = CO  H = -26.4 Kcal/mole CO +1/2 O2 = CO2  H = -67.6 Kcal/mole Reduction of After Burn Temperature with Promoted CO Combustion Component Temperature C Without Promoter With Promoter Typical Flue Gas 700 650 Dense Phase 660 675 After-burn  T +40 -15

54. De SOx Additive About 10% Sulfur in FCC feed gets deposited in the coke This sulfur in coke is oxidised to SO2(90%) and SO3(10%) in the FCC regenerator. Sulfur in Flue Gas Emissions are stringently restricted by emission norms DeSOx Additives help in reducing emissions of SOx An effective Sox reduction catalyst must oxidize SO2 to SO3 and form a sulfate. This sulfate has to be stable under regenerator conditions and be able to release the sulfur as sulfide in the reactor

55. Chemistry of SOx Reduction Reactions in Regenerator S(in coke) + O2 = SO2 2SO2 + O2 = 2SO3 SO3 + MO = MSO4 Reactions in the Reactor MSO4 + 4H2 = MO + H2S + 3H2O MSO4 + 4H2 = MS + 4H2O Stripper: MS + H2O = MO + H2S

56. S(in coke) + O2 = SO2 2SO2 + O2 = 2SO3 SO3 + MO = MSO4 MSO4 + 4H2 = MO + H2S + 3H2O MSO4 + 4H2 = MS + 4H2O MS + H2O = MO + H2S

57. SOx Reduction Catalysts MgO,Al2O3,MgAl2O4, La2O3 and CeO2 based catalysts are suitable for FCC unit DeSOx Ceria oxidises SO2 to SO3 SO3 is picked up as sulfate on MgO and Mg spinels Sulfur picked up in regenerator is stripped in the reducing atmosphere of the reactor.

58. Feed Metal Deactivation Ni and V present in heavy ends of the feed end in the catalyst Both Ni and V function as dehydrogenation catalysts in FCC reactor Relative dehydrogenation activity is expressed in terms of 4Ni+V Vanadium reacts destructively with zeolitic component of FCC catalyst Ni alters the selectivity to coke and gas yields

59. FCC Passivation Additives Ni Passivation is effective with only Antimony,Bismuth and Cerium based compounds. Compounds with active ingredients in Organic or Aqueous solvent is generally used XRD results suggest that Sb forms Ni-Sb solid solutions with high level of Sb on the Ni surface thus causing the passivation effect. Sn reduces the deletirious effect of V by forming inert compounds on the FCC catalyst surface.Sn/V complex is formed

60. FCC – Recent Trends

61. Changes in FCCU yields over the years Time Period1960197019801990 Design Features Cracking ModeBedRiser Riser with Rapid disengaging Combustion Mode Partial Complete Feed – Catalyst Mixing Poor Good Catalyst TypeAmorphousRE Y ZeoliteUSY ZeoliteUSY Zeolite with active Matrix Yields Wt% C 2 - LPG Gasoline Cycle oils Coke RON 5.0 18.7 45.4 21.5 9.4 92.0 3.8 17.3 49.8 21.7 7.4 91.0 4.0 17.9 50.9 21.8 5.4 92.5 3.3 17.9 52.5 21.5 4.8 93.0

62. IMPROVEMENTS IN FCC YearAvg.Feed processed (in tons)per kg of catalyst Max. Concarbon of feed Avg. conversion for VGO 1950 0.5 1% 62% 1975 1.1 2.5% 73% 2000 2.0 7.5% 79% Source : Akzo Nobel (Albemarle) catalyst data

64. Fluid Catalytic Cracking Catalysts– Future Trends More Resid Cracking and Deep Catalytic Cracking application will require new zeolite materials with larger pores – metal tolerance required More FCC units will be designed for Petrochemical feedstocks – Additive usage will increase - More selective Additive for Propylene/Butylene will be required. Development of Newer Additives for meeting product quality will be required – Sulfur/Olefins