INEOS TECHNOLOGIES EDC OXYCHLORINATION CATALYSTS Vinyl India 2015 Scan to visit Ineos Technologies website Follow us on: 1
INEOS Technologies Vinyls Solutions to the Vinyls Industry. We develop and license worldwide our EDC / VCM & PVC technologies. INEOS: 3rd largest Vinyls producer. 70+ yrs experience in the Vinyls sector Worldwide scale PVC & EDC pilot plants. Multi-million tons operating Globally under INEOS Licenses. We provide lifetime services to our Customers. 2
Pore Distribution Cumulative Pore Volume INEOS Technologies Vinyls Solutions to the Vinyls Industry. Our target is to Add Value for our Customers. PVC Pilot Plant Develop innovative additives for PVC & catalysts for Oxychlorination. Optimise clients operating / process conditions. Develop optimised PVC recipe. Dedicated Customer support.: - Application trial. - Additive / catalyst testing. - Process development. - Customer Specific studies / trainings. EDC Pilot Plant 3
The Balanced EDC/VCM Production Process C 2 H 4 + 0.5 O 2 + 2 HCl C 2 H 4 Cl 2 + H 2 O FIXED & FLUID BED 2 C 2 H 4 Cl 2 2 C 2 H 3 Cl + 2 HCl C 2 H 4 + Cl 2 C 2 H 4 Cl 2 HTC & LTC 4
WHERE INEOS CATALYST IN THE WORLD (PAST and PRESENT) Fixed Bed Fluid Bed INEOS Fixed Bed INEOS Fluid Bed (before SOLVIN INEOS JV) 5 This document is the property of INEOS Technologies (Vinyls) Limited and the information it contains is strictly confidential and may not be copied, used or disclosed without the express permission of Ineos Technologies (Vinyls) Limited.
Our EDC/VCM R&D team is located near Venice, Italy: Research & development of new Oxychlorination Catalytic systems (fluid and fixed bed) and related pilot testing Catalyst Production Control and Catalyst Quality Control Technical support for Customers (world-wide) and INEOS production plants (UK, Germany, Norway, Sweden) Optimization of Technolgies and Processes for Oxychlorination 6
Features Fluid Bed Oxy Pilot Plant 4m Oxychlorination reactor (Nickel 200), condensation system, on-line vent gas analyser and vent gas treatment Mass balance: Vent gas, Acidity, EDC purity 7
Fixed Bed Oxy Pilot Plant Features Two reactors On line vent gas analysis, off line analysis of EDC and water Fully automised under DCS control 8
R&D Catalysts: Oxychlorination Technologies HCl Conversion C 2 H 4 Selectivity to EDC Pressure Drop Catalysts Life HCl Conversion (C 2 H 4 conversion Air) C 2 H 4 Selectivity to EDC Fluid Dynamic behavior - Sticking Catalysts Losses Ethylene HCl, Oxygen Steam EDC + by-products Boiling Water RO TIC Catalyst Ethylene HCl EDC & By-Products air/oxygen 9
INEOS OXYCHLORINATION FIXED BED CATALYSTS AND DILUENT IVOC P CATALYSTS: P1D P2 - P3 - P3P (NEW) P1DT P2T P3T IVOD-1 STANDARD DILUENT IVOD-2F HIGH PERFORMANCE DILUENT 10
Fixed Bed oxychlorination catalysts Key Factors : INEOS catalysts CAN BE SUPPLIED ALREADY MIXED rotation: 3 min MIXING HAS TO BE OPTIMIZE TO MAXIMISE HOMOGENEITY 70% 60% 50% 40% % wt cat 30% 20% 10% 0% A B C D E F S1 S3 sampling line sampling point rotation: 6 min A B C D E F S2 S1 S2 80% 70% 60% 50% % wt cat 40% 30% 20% 10% 0% A B C D E F S1 S3 sampling line sampling point rotation: 9 min 80% 70% 60% 50% % wt cat 40% 30% 20% 10% 0% A B C D E F S1 S3 sampling line sampling point 11
C Fixed Bed oxychlorination catalysts Key Factors : INEOS catalysts CAN BE SUPPLIED ALREADY MIXED 280 Simulation of a 1st reactor (O2 Technology) TEMPERATURE PROFILE 270 260 250 240 230 220 210 0 0.5 1 1.5 2 2.5 3 3.5 z Normal Loadign Pattern - gas Temp 6% of catalysts in TOP zone - gas Temp 6% of catalysts in TOP zone - cat Temp Normal Loadign Pattern - cat Temp NOT HOMOGENEOUS MIXING DIFFERENT CONDITIONS IN DIFFERENT TUBES 12
Fixed Bed oxychlorination catalysts Key Factors : INEOS catalysts CAN BE SUPPLIED ALREADY MIXED Mixing is an important step to ensure homogeneity of activity and then good performance in terms of catalysts life and selectivity. INEOS has optimized the production of mixed materials (CATALYST IVOD-1/IVOD-2F) than can be loaded as they are directly in the reactor 13
Fixed Bed oxychlorination catalysts Key Factors : PRESSURE DROP Reactor's Pressure Drop Second Reactor Pressure Drop UP TO 20% REDUCTION 60% 70% 80% 90% 100% % capacity INEOS CATALYSTS 5x5 mm standard Catalyst LOW PRESSURE DROP HIGH CAPACITY 14
Reactor Pressure Drop Fixed Bed oxychlorination catalysts Key Factors : PRESSURE DROP TUBE'S DISTRIBUTION First Reactor Pressure Drop 50% 70% 90% 110% 130% 150% Capacity New IVOD-2F Diluent Standard IVOD-1 diluent TUBE PACKING QUALITY STANDAR DILUENT NEW DILUENT The new high performance IVOD-2F diluent: -Low dp for High Capacity Plant -Higher reactor homogeneity for better performance at harded conditions 15
Fixed Bed oxychlorination catalysts Key Factors : CATALYST LIFE C % of pellet with Coke Temperature profile and coke formation 290 270 250 230 210 190 170 150 0 50 100 150 200 z (reactor depth, 0=inlet) New Generation - Temperature Profile New Generation - coke formation OLD Generation - Temperature Profile OLD Generation - coke formation LOW FOULING RATE LOW COKE PRODUCTION RATE LONG CATALYST LIFE 16
Fixed Bed oxychlorination catalysts Key Factors : CATALYST LIFE Pressure Drop (catalyst integrity) Steam to O2 ratio Reactor Outlet Temperature Reactor's Pressure Drop THREE YEARS RUN WITHOUT CHANGE CATALYSTS LOW FOULING RATES and LONG STABLE ACTIVITY Time on Stream CASE B CASE A Catalyst's Activity 250 HIGH CAPACITY FOR LONGER TIME THREE YEARS RUN WITHOUT CHANGE CATALYSTS HIGHER FLEXIBILITY TO BUSINESS REQUIRMENTS Steam to O2 ratio Time on Stream Reactor out Temperature 200 17
Reaction Rate Reaction Rate Fixed Bed oxychlorination catalysts Key Factors : ACTIVITY AND SELECTIVITY Effect of Cu - Additive ratio on Activity Effect of Cu exposed on Activity 1.0 0.8 0.6 0.4 0.2 0.0 Additive / Cu mol/mol 1.0 0.8 0.6 0.4 0.2 0.0 Copper Exposed (CO probe molecule) - QUALITY OF RAW MATERIAL: HIGH PURITY ALUMINAS - CHEMICAL COMPOSITION: COPPER ADDITIVE - SURFACE AREA AND PORE VOLUME DISTRIBUTION OF ACTIVE SITES 18
Fixed Bed oxychlorination catalysts Key Factors : ACTIVITY AND SELECTIVITY % Ethylene to COx 0.6% INEOS CATALYSTS - PILOT PLANT RESULTS 0.5% 0.4% 0.3% 0.2% 0.1% 0.0% 98.6 98.8 99.0 99.2 99.4 99.6 99.8 100.0 HCl Conversion OLD GENERATION NEW GENERATION 19
Ethylene to COx Fixed Bed oxychlorination catalysts Key Factors : ACTIVITY AND SELECTIVITY INEOS Catalysts - Industrial Results OLD GENERATION HCl conversion NEW GENERATION EXCELLENT RESULT CAN BE OBTAINED AT CAPACITY 10-20% ABOVE THE DESIGN 20
INEOS Oxychlorination Fluid bed catalysts Ineos Fluid bed catalyst portfolio 21
INEOS Oxy Catalysts Main physical-mechanical features of our Catalysts Average Particle Size (microns) 55 Less than 20 microns (%) 2 Bulk Density (g/cc) 1.00-1.20 Very Low fines and moisture content INEOS fluid bed catalysts can be also added to the already present charge of catalyst. Mechanical properties and formulation allow mixing during top up without adverse influence on the reactor functioning. 22
Main Fluid Bed Catalyst Aspects Catalyst agglomeration (sticking) Active catalyst converts HCl and prevents the loss in fluidization Corrosion Accumulation of Iron increases the by products formation. 23
Main Fluid Bed Catalyst Aspects Erosion Support hardness Catalyst losses The attrition test measures the tendency of a catalyst to generate fines. Top up of the catalyst catalyst is periodically added to the reactor depending on the catalyst losses. 24
Fluid Bed Oxychlorination Catalysts: Activity High reactant conversion: Ethylene Conversion > 99.5% HCl Conversion > 99.5% 50% increase in rate same performance 25
Fluid Bed Oxychlorination Catalysts: Selectivity High Selectivity Reduced combustion rate EDC Purity > 99% (V/V) 26
Fluid Bed Oxychlorination Catalysts: Stability High reaction stability/ No sticking Able to operate at different reactant ratios without any fluidization problem 27
What impact could have Fluid Bed Catalysts? Example & some assumptions: 300 ktpa VCM plant, 50 tons of catalyst hold-up, 15tons/year of catalyst losses Operating rate 90% Assume cost of ethylene 0.75 USD/kg Assume EDC margins 100 USD/ton Assume 100% Ineos FB Catalyst and an increase in Ethylene Yield by 5% 28
What impact could have Fluid Bed Catalysts? Results: Increasing output by 10%: more than 2 M USD/yr Oxygen+ethylene saving: more than 0.65 M USD/y Caustic savings: more than 0.25 M USD/y Increase of the operating rate estimated in 5 days of more production: 0.29 M USD/y 29
Our Technical Service Offer for FIXED AND FLUID BED CATALYSTS On-site plant visit by INEOS catalyst expert to improve plant optimisation and discussions Training (fluid bed) of plant personnel during 3 to 5 days in our R&D facilities and pilot plant in Italy. Pilot plant tests at particular operating conditions following customer requests Studies concerning: Metal analysis (poisoning), Particle size distribution, Catalyst hardness (attrition/erosion) and mechanical strength, Stickiness, Catalyst activity-pilot plant testing, Operating parameters optimization, 30