TAKREER RESEARCH CENTRE Resid fluid catalytic cracking catalyst selection Presented by: Gnana Pragasam Singaravel, TAKREER Research Centre The 3 rd Saudi International Petrochemical Technologies Conference 2015, 5 th -6 th May, 2015, Riyadh, Saudi Arabia
Contents TAKREER overview Ruwais Refinery Expansion and RFCC project RFCC Catalyst Selection Process Summary & Conclusion 2
TAKREER Crude Gas Final Products Safety is our Culture
Abu Dhabi Oil Refining Company (TAKREER) (OVERALL) RR (E) RR (W) Refineries ADR TRC R&D HQ 4
Abu Dhabi Refinery (ADR) FEED PRODUCTS CRUDE OIL CONDENSATE ABU DHABI REFINERY 85,000 BPSD LPG NAPHTHA JETFUEL GASOIL RESIDUE 5
Ruwais Refinery East (RRE) FEED PRODUCTS CRUDE OIL CONDENSATE RUWAIS REFINERY EAST 420,000 BPSD LPG NAPHTHA GASOLINE JETFUEL GASOIL FUELOIL/RESIDUE GREEN DIESEL PLANT ENVIRONMENTAL QUALITY REGULATION PROJECT PRODUCES ULTRA LOW SULFUR GASOIL WITH SULFUR CONTENT <10 PPM 6
Ruwais Refinery West (RRW) FEED PRODUCTS CRUDE OIL RUWAIS REFINERY WEST 417,000 BPSD RFCC BLOCK UNITS 127,400 BPSD ATMOSPHERIC RESIDUE LPG NAPHTHA JETFUEL A-1 ULSD Strategic alliance with Borouge POLYMER GRADE PROPYLENE UNLEADED GASOLINE SLURRY TO CB&DC SRU & TGTU SULFUR 7
RFCC section 8
RRW-Expansion -Main Objective Increase in ADNOC s Refined Product share Bottom of Barrel Upgrading (CBDC) RR Expansion Project (RR-West) Environmental & Quality Specifications Meeting stringent product quality leading to harmful emission reduction Integrity & Diversity Production of high value products like Propylene, Carbon Black & Anode grade Coke STRATEGIC INTEGRATION
Mission & Objectives of TRC Vision Mission - To support and develop TAKREER core refining activities as well as assist in Technology Transfer and Human Resources Development in collaboration with local and international Institutes and Universities Objectives - To become a leading Research Centre in the field of refining technology, process and product development - To be a Technology Provider for Takreer refineries by supporting and developing Takreer core refining activities TRC - To assist in Technology Transfer and Human Resources Development in collaboration with other Institutes and Universities. Refineries Petroleum Institute (PI) UAE University, Masdar Institute (MI), Borouge Innovation Centre, Future Upstream Research Centres 10
Overview Fluid catalytic cracking (FCC) catalysts account for 40 to 45% of worldwide gasoline production. Catalytic cracking is an essential process for gasoline production and base chemicals, such as propylene. Currently, more than 450 fluid catalytic cracking (FCC) plants are operated worldwide, consuming about 2000 metric tons of catalyst per day. Total EMEA market test by catalyst selection is 65% 11
Why? & How? Catalyst selection----- Why? Catalyst deactivation----- How? Test -----How and why? Evaluation----How? Commercial ecat? 12
Laboratory catalyst selection study Catalyst selection based on a laboratory evaluation is favored because Physical properties and yield predictions accuracy A common test procedures/protocols irrespective of catalyst supplier, i.e. ACE testing, deactivation, attrition testing etc Plant trial conclusion is a significant change-out of the inventory (> 60%) ACE R+MM Laboratory catalyst selection study is the only way CMI/CDU 13
Laboratory catalyst selection study. Comparison based on same feedstock quality and unit operation catalyst supplier could not achieve in practice Hardware Changes could make a plant trial meaningless (stripper/feed nozzle deterioration...) High economical risk due to undesired changes in the yield pattern as well as impacts on unit equipment like expanders Compare different catalyst technologies on a comparable basis 14
Deactivation Methods Deactivate the catalyst Mitchell Method (MM) Incipient wetness impregnation Steam deactivation Cyclic Metals Impregnation (CMI) Multiple cycles of cracking with metals spiked feedstock and regeneration Optionally additional steaming Cyclic Propylene Steaming (CPS) Incipient wetness impregnation Ageing in a redox environment Shell Impregnation-Spray Metallation (SM) Ageing in a redox environment or Optionally additional steaming 15
Deactivation procedure Deactivation protocols MI CMI/CDU CPS SM Commercial Environment Inert /oxidising Cyclic redox Cyclic redox Cyclic redox Cyclic redox Effect on vanadium +5 +3 to +5 +3 to +5 +3 to +5 +3 to +5 Effect on nickel +2 +2 to 0 +2 to 0 +2 to 0 +2 to 0 Metals distribution Uniform / bulk Shell Uniform / Shell Shell coating Shell Metals age distribution Uniform Nonuniform Uniform Uniform Nonuniform Application Easy Good Difficult Bottleneck Easy Very good Easy Very good - - 16
SM vs CMI/CDU Spray metallation (SM) Easy to implement and scale-up Matches e-cat activity and yields Accurate deactivation of metals traps Easy to tailor to match specific unit Very robust method Cyclic metals impregnation (CMI/CDU) More time-consuming No apparent advantages in matching properties or yields Lower sample throughput Less robust because of control and longer duration 17
Turning point Product quality requirements Special Refinery Requirements Product value change Supply contract expiration Feed changes Catalyst Reformulation New Catalyst Technology Unit Revamp 18
When the process released Research Centre Physical and chemical properties Deactivation-CDU/SM ACE/SCTRT Process optimisation Simulation & modeling Purchase and contracts Quantity Logistics Negotiation Quality assurance INPUT Coordination and operational management OUTPUT Refinery Turnaround Refinery Objectives Refinery Margins Unit constraints Refinery integration Planning and programming Crude oil quality Market demand Oil prices Refinery Margins 19
Catalyst selection is called for Catalyst coordinator Operation, Process, procurement, Contracts Business management group -Goals and scope Product values selection -Base case Initiator Evaluation Feed, fresh, ecat and experimental parameters Communicates to vendors 20
How do it for best assure? Monitoring, scale up and technoeconomic value Optimum goal Model Integration Simulated integration Pilot plant and laboratory evaluation Match with commercial unit 21
Factors for the catalyst Fresh catalyst Physico-chemical Characteristics Deactivation by metal -steaming -Oxidation/reduction ABD, TSA., ZSA, MSA, mipv, APS, UCS, Attrition Activity Selectivity stability Temperature Time Cycle length Characteristics Activity Selectivity stability 22
Technical process finish. Review of experimental conditions and constraints Refinery margins calculations Commercial offer from catalyst suppliers Matrix selection by Business management team New contract agreement conditions New catalyst replacement 23
Deciding on the best catalyst selection Case study Implications of ACE test data Low Z/M catalyst make higher coke with matrix activity and increased slurry cracking Equilibrium catalyst test by ACE reveals the low Z/M catalyst produces 0.9% of higher coke than high Z/M catalyst The coke factor is unrealistic of what is happening in the commercial unit Kinetic Coke, wt% 90 80 70 60 50 40 30 20 10 0 4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 Conversion 1 2 3 4 5 Z/M Dry gas LPG Gasoline LCO Bottom Coke Lab Ecat Refinery Ecat Refinery Ecat1 24
Summary & Conclusion Proper catalyst selection and minimize risk Physical Testing issues in the commercial unit from problematic attrition resistance as well as fluidization properties. Catalytic bench scale deactivation in a robust protocol Validation of test results by checking mass balances and raw data dependencies Yield prediction based on constant coke yield results enables comparison at constant feed rate and heat balance. Activity retention is considered at constant CAR Optimization of the operation by selecting the most economic catalyst technology 25
Thank you 26