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Reforming: Update on Catalysts & Technologies
Thierry Leflour
1
Agenda
• Semi-regenerative applications • Reforming catalyst portfolio
• Texicap™: optimum usage of catalyst inventory
• CCR Reforming technology updates • Catalyst breakthrough
• CCR technology
• Adsorbents Selection
2
Fixed Bed Reforming Catalysts : Current products
Re / Pt 0 1 1.6 1.8
Target Unit Cyclic SR SR SR
Stability Good Best
S tolerance Best Good
Low density
Standard density
Family of Multi-Promoted Fixed Bed Catalysts
RG 532 RG 582 RG 682
P 15 PR 15 PR 36 PR 30
P 152 PR 150 PR 156 New
3
Main benefits of new family
• High yields in a wide range of operating conditions
• Same activity as previous generation
• Outstanding stability
• Low cost to fill
Improved Profitability
4
Characteristic of new series (I/II)
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 PR 150
Same activity but higher stability with 20 % less coke production
5
Characteristic of new series (II/II)
PR 15 New
H2 (wt %)
Base +0.1
C5+
(wt %) Base +1.5
Time (hours)
82
83
84
85
86
87
88
48 72 96 120 144 168 192 216 240 264 288
Normalized C5+, wt % PR 15 PR 150
Highly Selective Catalyst 6
Agenda
• Semi-regenerative applications • Reforming catalyst portfolio
• Texicap ™ : optimum usage of catalyst inventory
• CCR Reforming technology updates • Catalyst breakthrough
• CCR technology
• Adsorbents Selection
7
B o l t e d m e t a l s h r o u d a n d c o v e r
Catalyst volume increase
With TexicapTM
Catalyst Dead Space
TexicapTM: Optimum Usage of Catalyst
Without TexicapTM
High coke deposit
Low coke High activity
High coke deposit
Low coke deposit High coke
Poor activity
Low coke deposit
Risk of high ΔT during regeneration
8
TexicapTM: What does it look like ?
Engineered refractory composite (Asbestos-free)
Scallops
Texicap
• Strong & Impermeable : withstands regeneration conditions
• First installation operating for more than 20 years
More than 100 references 9
Benefits of TexicapTM
• All loaded catalyst fully active
• Easy option to allow capacity or severity increase
• Possibility of unit short loading
• Easy and safe regeneration
• Shorter time during loading
• Easier inspection
10
Agenda
• Semi-regenerative applications • Reforming catalyst portfolio
• Texicap ™ : optimum usage of catalyst inventory
• CCR Reforming technology updates • Catalyst breakthrough
• CCR technology
• Adsorbents Selection
11
Axens CCR Reforming Catalyst Portfolio
Application Gasoline Aromatics 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
Yields
Strength
Target Unit All All Competitor
Density High density Low density
CR 600s
AR 700s
PS 40
PS 100
12
Multipromoted Series Results
Previous Generation • Bi-promoted • Base Pt content
Axens’ New Series • Multi Promoted • Reduced Pt content
C5+ yields
Pilot testing Time (screening on fixed bed reactor)
With reduced Pt content, C5+ yields increased by 1.5% and 25% coke make reduction
Improved Yields
Improved stability
13
Multipromoted Series Benefits
• High selectivity with no penalty on activity
• High hydrothermal stability
• Intrinsically good Cl retention
• Robustness of the catalyst :
Example of a unit loaded with CR 600 and suffering from lack of Cl injection
14
Robustness of the Catalyst (I/III)
Catalyst and reformate color during chloride injection issue
After fixing the Chloride injection issue
Pt dispersion ~ 30 %
Pt dispersion 100 %
15
2
4
6
8
80
82
84
86
88
90
92
94
96
98
100
180
190
200
210
220
230
240
250
260
270 +12
+10
+8
+6
+4
+2
Base
-2
-4
-6
-8
+20
+10
Base
-10
-20
-30
-40
-50
-60
-70
Catalyst recovers after strong Pt agglomeration
Impact on Yield & Coke (II/III)
Coke (% wt) DT (°C) C5+ (% wt)
Chlorine injection problem solved
16
Significant activity recovery after Cl injection back on-line
4 days
2 RON
-60
-40
-20
Base
20
40
1-Jan 6-Jan 11-Jan 16-Jan 21-Jan 26-Jan 31-Jan
Actual WAIT, F
-6
-4
-2
Base
2
4 RON
WAIT DEG F
RON
Problem of Cl injection solved
Robustness of Catalyst (III/III)
17
Agenda
• Semi-regenerative applications • Reforming catalyst portfolio
• Texicap ™ : optimum usage of catalyst inventory
• CCR Reforming technology updates • Catalyst breakthrough
• CCR technology
• Adsorbents Selection
18
0
10
20
30
40
50
60
70
80
90
100
110
0.0
0.1
0.1
0.2
0.2
0.3
0.3
1970 1975 1980 1985 1990 1995 2000 2005 2010
CCR Licensing Cumulative
Capacity, Mbpsd Cumulative Number
of references
as of February 2013
World Total: 107 Licenses
Cumulative Capacity: ~ 2.8 Mbpsd
Over 100 Licensed units ranging from 8,000 to 90,000 bpsd ULP designs
19
Axens’ CCR Technology
Regenerator
Reactors and Heaters
Recovery
System
H2 rich
gas
Reformate
to Stabilizer
Feed
Net Gas
Compressor
Recycle
Compressor
Open source, DCS controlled catalyst
circulation and regeneration
20
Side-by- Side Arrangement Merits
Easy maintenance
Easy engineered, low-cost technology set-up
2 000 kTPA
Low investment structure
Short transfer lines
21
Primary Burn
Finishing Burn
Calcination
Oxy- chlorination
Spent Catalyst
Regenerated Catalyst
Dry Combustion Gas
Air
Air
Oxychlorination Calcination Gas
Chloriding Agent + water
Optimum catalyst “protection”
Regenerator Section: RegenC-2
Dry Burn Loop Optimum Chlorine Management
22
Regeneration in CCR Units
90
110
130
150
170
190
210
230
0 365 730 1095 1460 1825 2190 2555 2920 3285 3650
DRY BURN LOOP
WET BURN LOOP
Graph developed from catalyst operation in a non-Axens CCR unit
specific surface area
(m2/g)
time on stream (days)
Evolution of Catalyst Specific Surface Area
23
Agenda
• Semi-regenerative applications • Reforming catalyst portfolio
• Texicap ™ : optimum usage of catalyst inventory
• CCR Reforming technology updates • Catalyst breakthrough
• CCR technology
• Adsorbents Selection
24
Purification in Reforming
for semi-reg unit 25
Main Contaminants
Stream Reformate downstream
reaction section
Regeneration of
the catalyst
HN upstream reaction section
Origin
During operation the Cl is removed from the catalyst
and goes in the rich gas and reformate stream
Coke burning Naphtha
Impact
Downstream unit catalyst poisoning and Equipment
corrosion
irreversible
Life time reduction
irreversible
Isomerization catalyst inhibition + PtS formation (Reduce unit cycle length
for fixed bed)
reversible
Adsorbents AxTrap 801,
AxTrap 857, AxTrap 858
AxSorb A » Regeneration Gas Drying
» Calcination Air Drying
AxTrap 405
HCl Water Sulfur
26
ZnO based
material
Promoted
alumina
AxTrap
858
Reformate stream (180°C)
HCl Removal in Gas & Liquid Phases
Hydrogen stream (30°C)
Molecular sieve
Standard alumina
ZnO
based
material
AxTrap
801
AxTrap
857
Low cost products Promoted alumina High performance
product
Promoted
alumina
Octanizing / Aromizing • 107 licensed units ULP, side by side designs, from
maximum gasoline to BTX mode
• More than 40 awards since 2005
• 2.8 MBPSD cumulated capacity
Superior yields
Stable and robust
Low Pt inventory
Products
Low investment cost design
Superior Regen
C2 concept
Technology
World-class site services Operator training
Web-based optimization and tracking tools
Services
Aromizing / Octanizing • Catalysts
• Adsorbents
28