1_Mohan Lal.pdf - World Petroleum Council

ADVANCES IN REFORMING CATALYSTInternational Refining Seminar“Refining Challenges and Way Forward”Organised by Petroleum Federation of India16 th -17 th April, 2012New Delhi (India)Mohan LalAxens India1

March 2011 Acquisition of thereforming business of Criterion corporationWillow Island,West Virginia, USASalindres, France• Each Heritage catalyst produced within heritage organization• On-going cross production trials• Different paths lead to quality products: mechanical strength,hydrothermal stability, chlorine retention• Great improvement potential from experience sharing2

Merger status• Current situation• Axens & Criterion legacy products still available• On going process for• Portfolio consolidation• New products launching3

What do Customers Look For ?Customer Targets• Proven and reliable catalyst• Improved economics• Low cost-to-fill• High hydrogen & Reformateproduction or aromaticsproduction• Low operating cost• High StabilityAxens’ Solutions‣ Homologated by Majors‣ More than 200 references withpromoted catalyst‣ Optimal Pt content & Loadingdensity‣ Minimised side reactionsUse of promoted catalyst‣ High chloride retention‣ High mechanical resistance‣ Stable surface area‣ Stable platinum dispersion‣ Low coke make catalyst4

Fixed Bed ReformingCatalysts5

SR & Cyclic section• Current portfolio• New productsTA 1 – CR 607Client technical assistance• Development• Summary• Reactor technology6

Fixed Bed Reforming Catalysts Established ProductsThe largest family of Multi-Promoted Fixed Bed CatalystsRe / Pt 0 1 1.3 1.6 1.8Target Unit CY SR/CY SR/CY SR SRIncreased StabilityBetter S toleranceUnconstrained UnitRG 532 RG 582 RG 682Increased ActivityHigher DensityP 15 PR 15 PR 30RG 5867

Fixed Bed Reforming Catalysts New ProductsThe largest family of Multi-Promoted Fixed Bed CatalystsRe / Pt 0 1 1.3 1.6 1.8Target Unit CY SR/CY SR/CY SR SRIncreased StabilityBetter S toleranceUnconstrained UnitIncreased ActivityHigher DensityNewPR 33 PR 36New8

New Reforming Catalysts• Higher catalyst stabilityPR 15PR 33PR 36 ; PR 30P/N/A = 60/24/13 % wt11

New Reforming Catalysts• Higher yields stabilityPR 36 ; PR 30PR 15P/N/A = 60/24/13 % wt12

Outcome• The PR 33 & PR 36 catalysts provide• High catalyst performances• Selectivity & stability• Fully regenerable• At the lowest precious metal content• The highest NPV for fixed bed application13

SR & Cyclic Section• Current portfolio• New productsTA 1 – CR 607Client technical assistance• Development• Summary• Reactor technology14

Nearing Commercialization• The highest selectivity with a maximum C 8aromatics production at constant catalystactivity15

Fixed Bed Reforming CatalystsNew ProductsThe new family of multipromoted catalystRe / Pt 0 1 1.6Target unit CY SR/CY SRIncreased stabilityBetter S toleranceHigher densityP 152 PR 150 PR 156We call them PR as we initially focus on high density carrier16

New SeriesBalanced version530Norm T, Deg C PR 15 New5255205155105055004954900 24 48 72 96 120 144 168 192 216 240 264 288Time (hours)Same activity but higher stability20 % less coke17

New SeriesBalanced versionNormalized C 5+ , wt % PR 15 New888786H 2(wt %)PR 15NewBase +0.1858483H 2(scfb)C 5+(wt %)Base +60Base +1.58248 72 96 120 144 168 192 216 240 264 288Time (hours)Max selectivity catalyst18

New SeriesBalanced version32.0A8, wt %PR 15NewPR 15New31.531.030.5A6(wt %)A7(wt %)Base BaseBase +0.5130.029.5A8(wt %)Base +0.6729.048 72 96 120 144 168 192 216 240 264 288Time (hours)Higher C 8 aromatics yield catalyst19

Axens Fixed Bed Catalyst Advantages• RG/PR catalysts are used by majors oil companies• More than 200 references with promoted catalyst• Loading density adjusted to comply with customer needs• The highest selectivity• Fixed bed reforming catalysts are Pt / Re based therefore in order tochange the yields we need to add something new‣ Promoted catalyst• The highest stability• Pt sintering hindered with promoter• Longer cycles• Outstanding surface stability• Longer life• The highest chloride retention20

Axens Fixed Bed Catalyst Advantages Selectivity• Side reactions• Hydrocracking linked to very acidic sites• Modified carrier• Hydrogenolysis linked to metal activity• Modified metals function• Promoter serves 2 roles• Lower C 3 & C 4 production• Lower C 1 & C 2 productionHigher hydrogen and C 5 +yields21

CCR ReformingCatalysts22

CCR Development Methodology• For 30 years the CCR catalyst market has been almostfully dominated by Pt/Sn• Any improvements maintaining the same formulation is verydifficult• The market still wants higher yields• Mainly hydrogen• Mainly aromaticsNeed for new catalyst formulation23

Prerequisite for the Formulation• The formulation needs• To be fully regenerable with standard equipment• The catalyst needs to keep at least the same• Chloride retention• Mechanical properties• Surface area stability needs to be improved to• Extend catalyst life• Ensure higher chloride retention throughout entire service life• Reduce production of fines24

Chemistry OptimizationNew Promoters developed to1. Increase catalyst selectivity by minimizingthe cracking reactions & ring openingHigher H 2 & C 5+ yields2. Increase catalyst stability by minimizing coke deposit on the catalystAllow to operate at lower recycle gas ratiosYields increaseReduction of utility consumption3. As topping on the cake - the Pt content has been reduced while catalyststability has increasedLower cost25

Axens Licensed Units in OperationToday: 40 units in operation26

Criterion Legacy & Axens CCR Catalyst in Non AxensUnits27

Criterion legacy & Axens CCR Catalyst in Non AxensUnitsAxens design ; Non Axens designAlmost 100 units in Operation28

Axens CCR Reforming Catalyst PortfolioCR 600’s AR 700’s PS 40 PS 100Application Gasoline Aros Gasoline / AromaticsPt, wt% 0.25 0.30 0.29 0.29PromotersSn + Others (Multi-Promoted)Moving bed density,t/m 3 0.65 0.65 0.54 0.54Main AttributesYieldsStrengthActivityStrengthActivityStrengthActivityYieldsStrengthTarget Unit All All CompetitorHigh DensityStandard Density29

CCR Reforming Standard Density CatalystPS-40: Top performer for over 10 years!Set the Standard for Performance Excellence.C 5+ yield: 1.0 -1.3 vol% more,H 2 Yield: 0.15 - 0.2 wt% more,Feed Thru-put: 15 -30% moreCoke Lay-down: 20–30% less,Cl Consumption: 10-30% less,Make Up Catalyst: 50-60% lessMore than 40 Non-Axens Design Units Supplied Worldwide30

CCR Reforming Standard Density Catalyst31

Evidence of HigherSurface Area RetentionSpecific surface area[m2/g]• Axens’ CR 600 & AR 700 provide the bestsurface area retention220200180160140120Sample A CR 607Pt/SnCR 600≈ 20 m 2 /g0 100 200 300 400TOS [h]• Operating conditions : Mixture of N 2 & H 2 O• 20% vol. water, at 650°C• Surface loss• Pt/Sn• ∆Surface = 55 m²/g• CR 607• ∆Surface = 22 m²/gHydrothermalstability has beenimproved by afactor 232

Summary of Improvements New GenerationCatalysts• Better yields• Hydrogen + 0.1 wt%• Reformate + 1 wt%• Coke make decreased by +30 %• Fully regenerable with standard regenerator• Surface area stability improved by a factor 2• Lower platinum contentTargets are achieved33

New Developments Standard Density CatalystPS New 100Available in 2012!•The result from the combination of Axens & Criterion’s catalyticReforming technology. Leaders in catalytic formulations andsuperior Alumina Support Technology.• Ultimate Selectivity.• Improved Activity for units with no pinninglimitations.•Same Physical Characteristics as PS-40:•Lower Attrition Rates•Lower Fines make•Surface Area Retention•Chloride Retention34

CCR Reforming High Density Catalyst• Reasons to justify High Density Catalysts• Activity constraints• Fire Heater limitations• High skin temperatures• High WAIT• Pinning constraints35

Summary• Axens & Criterion Reforming business havemerged• The PR & PS Catalyst are still available• New products are coming out soon• R&D is working to take all the benefit of thetwo corporation knowledge36

Thank You for your attentionVisit us at : http://www.axens.net37