advances in reforming catalyst - world · pdf file1 advances in reforming catalyst....
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ADVANCES IN REFORMING CATALYSTInternational Refining Seminar
“Refining Challenges and Way Forward”Organised by Petroleum Federation of India
16th -17th April, 2012 New Delhi (India)
Mohan LalAxens India
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March 2011 Acquisition of the reforming business of Criterion corporation
Salindres, FranceWillow Island, West Virginia, USA
• 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 sharing
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Merger status
• Current situation• Axens & Criterion legacy products still available
• On going process for • Portfolio consolidation• New products launching
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What do Customers Look For ?
• Proven and reliable catalyst
Axens’ SolutionsHomologated by MajorsMore than 200 references with
promoted catalyst
Customer Targets
Optimal Pt content & Loading density
Minimised side reactionsUse of promoted catalyst
• Improved economics
High chloride retentionHigh mechanical resistance
Stable surface area Stable platinum dispersionLow coke make catalyst
• High Stability
• Low cost-to-fill • High hydrogen & Reformate
production or aromatics production
• Low operating cost
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Fixed Bed Reforming Catalysts
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TA 1 – CR 607 Client technical assistance
• Current portfolio
• New products
• Development
• Summary
• Reactor technology
SR & Cyclic section
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Fixed Bed Reforming Catalysts Established Products
Re / Pt 0 1 1.3 1.6 1.8
Target Unit CY SR/CY SR/CY SR SR
Increased Stability
Better S tolerance
Unconstrained Unit
Increased Activity
Higher Density
The largest family of Multi-Promoted Fixed Bed Catalysts
RG 532 RG 582 RG 682
P 15 PR 15 PR 30
RG 586
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Fixed Bed Reforming Catalysts New Products
Re / Pt 0 1 1.3 1.6 1.8
Target Unit CY SR/CY SR/CY SR SR
Increased Stability
Better S tolerance
Unconstrained Unit
Increased Activity
Higher Density
The largest family of Multi-Promoted Fixed Bed Catalysts
PR 33 PR 36
New New
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Fixed Bed Reforming Catalysts Available Products
Re / Pt 0 1 1.3 1.6 1.8
Target Unit CY SR/CY SR/CY SR SR
Increased Stability
Better S tolerance
Unconstrained Unit
Increased Activity
Higher Density
The largest family of Multi-Promoted Fixed Bed Catalysts
RG 532 RG 582 RG 682
P 15 PR 15 PR 33 PR 36 PR 30
RG 586
New New
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TA 1 – CR 607 Client technical assistance
• Current portfolio
• New products
• Development
• Summary
• Reactor technology
SR & Cyclic Section
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New Reforming Catalysts
P/N/A = 60/24/13 % wt
PR 33 PR 36 ; PR 30PR 15• Higher catalyst stability
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New Reforming Catalysts
• Higher yields stability
PR 36 ; PR 30
PR 15
P/N/A = 60/24/13 % wt
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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 application
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TA 1 – CR 607 Client technical assistance
• Current portfolio
• New products
• Development
• Summary
• Reactor technology
SR & Cyclic Section
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Nearing Commercialization
• The highest selectivity with a maximum C8 aromatics production at constant catalyst activity
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Fixed Bed Reforming Catalysts New Products
Re / Pt 0 1 1.6
Target unit CY SR/CY SR
Increased stability
Better S tolerance
Higher density
The new family of multipromoted
catalyst
P 152 PR 150 PR 156
We call them PR as we initially focus on high density carrier
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New Series Balanced version
490
495
500
505
510
515
520
525
530
0 24 48 72 96 120 144 168 192 216 240 264 288
Time (hours)
Norm T, Deg C PR 15 New
Same activity but higher stability20 % less coke
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New Series Balanced version
PR 15 NewH2
(wt %)Base +0.1
H2(scfb)
Base +60
C5+
(wt %)Base +1.5
82
83
84
85
86
87
88
48 72 96 120 144 168 192 216 240 264 288
Time (hours)
Normalized C5+, wt % PR 15 New
Max selectivity catalyst
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New Series Balanced version
29.0
29.5
30.0
30.5
31.0
31.5
32.0
48 72 96 120 144 168 192 216 240 264 288
A8, wt %
PR 15 NewA6
(wt %)
Base Base
A7
(wt %)
Base +0.51
A8
(wt %)
Base +0.67
Time (hours)
PR 15 New
Higher C8
aromatics yield catalyst
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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 to change 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 retention
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• Side reactions• Hydrocracking linked to very acidic sites
• Modified carrier
• Hydrogenolysis linked to metal activity• Modified metals function
• Promoter serves 2 roles • Lower C3 & C4 production• Lower C1 & C2 production
Higher hydrogen and C5+ yields
Axens Fixed Bed Catalyst Advantages Selectivity
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CCR Reforming
Catalysts
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CCR Development Methodology
• For 30 years the CCR catalyst market has been almost fully dominated by Pt/Sn• Any improvements maintaining the same formulation is very
difficult
• The market still wants higher yields• Mainly hydrogen• Mainly aromatics
Need for new catalyst formulation
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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 fines
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Chemistry Optimization
New Promoters developed to
1. Increase catalyst selectivity by minimizing the cracking reactions & ring opening
Higher H2 & C5+ yields
2. Increase catalyst stability by minimizing coke deposit on the catalystAllow to operate at lower recycle gas ratios
Yields increaseReduction of utility consumption
3. As topping on the cake - the Pt content has been reduced while catalyst stability has increased
Lower cost
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Today: 40 units in operation
Axens Licensed Units in Operation
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Criterion Legacy & Axens CCR Catalyst in Non Axens Units
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Criterion legacy & Axens CCR Catalyst in Non Axens Units
Axens design ; Non Axens design
Almost 100 units in Operation
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Axens CCR Reforming Catalyst Portfolio
Application Gasoline Aros Gasoline / Aromatics
Pt, wt% 0.25 0.30 0.29 0.29
Promoters Sn + Others (Multi-Promoted)
Moving bed density, t/m3 0.65 0.65 0.54 0.54
Main Attributes Yields Strength
Activity Strength
Activity Strength
Activity Yields
Strength
Target Unit All All Competitor
CR 600’s AR 700’s PS 100
Standard DensityHigh Density
PS 40
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PS-40: Top performer for over 10 years! Set the Standard for Performance Excellence.
C5+ yield: 1.0 -1.3 vol% more,
H2 Yield: 0.15 - 0.2 wt% more,
Feed Thru-put: 15 -30% more
Coke Lay-down: 20–30% less,
Cl Consumption: 10-30% less,
Make Up Catalyst: 50-60% less
CCR Reforming Standard Density Catalyst
More than 40 Non-Axens Design Units Supplied Worldwide
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CCR Reforming Standard Density Catalyst
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Evidence of Higher Surface Area Retention
•
Axens’
CR 600 & AR 700 provide the best surface area retention
120
140
160
180
200
220
0 100 200 300 400TOS [h]
Spec
ific
surfa
ce a
rea
[m2/
g]
Sample A CR 607
CR 600
≈
20 m2/g
Pt/Sn
•
Surface loss•
Pt/Sn •
∆Surface = 55 m²/g
•
CR 607•
∆Surface = 22 m²/g
•
Operating conditions : Mixture of N2
& H2
O•
20% vol. water, at 650°C
Hydrothermal stability has beenimproved by a factor 2
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Summary of Improvements New Generation Catalysts
• 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 content
Targets are achieved
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New Developments Standard Density Catalyst
•The result from the combination of Axens & Criterion’s catalytic Reforming 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 Retention
Available in 2012!PS 100New
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CCR Reforming High Density Catalyst
• Reasons to justify High Density Catalysts
• Activity constraints• Fire Heater limitations
• High skin temperatures• High WAIT
• Pinning constraints
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Summary
• Axens & Criterion Reforming business have merged
• The PR & PS Catalyst are still available
• New products are coming out soon
• R&D is working to take all the benefit of the two corporation knowledge
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Thank You for your attention
Visit us at : http://www.axens.net