Engineering Fixed Bed Hydrocarbon Conversion Reactors to Control Pressure Drop Increases Dr. Ken J. Mills, Dr. Thomas Szymanski, Saint-Gobain NorPro Mohammed Q Raza, National Methanol Company, Ibn Sina Catalysts in Petroleum Refining & Petrochemicals KFUPM, Dhahran 16 – 17 November, 2008
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Engineering Fixed Bed Hydrocarbon Conversion
Reactors to Control Pressure Drop Increases
Dr. Ken J. Mills, Dr. Thomas Szymanski, Saint-Gobain NorPro Mohammed Q Raza,
National Methanol Company, Ibn Sina
Catalysts in Petroleum Refining & Petrochemicals
KFUPM, Dhahran16 – 17 November, 2008
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
The oil refining industry is under pressure
•
Oil refineries need to◦
Increase production
◦
Produce cleaner fuels◦
Utilize heavier and sourer feedstocks
◦
Reduce operating costs◦
Reduce energy consumption
Graded beds have been replaced by more advanced systems
Graded Denstone®
support media
Main catalyst (supplied by
others)
Feed
Denstone®
support media
The old way The new way
MacroTrap® media
Denstone® deltaP™support media
Main catalyst(supplied by
others)
Feed
HSA alumina ring
Pentaring bed topping media
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Major causes of pressure drop increase•
Deposition of entrained particulates◦
Tramp Iron – rust and other particles from upstream pipelines, heat exchangers etc.
◦
Carbon particles from poorly adjusted burners upstream◦
Attrited fluid catalytic cracking catalysts not trapped by the cyclone
•
Deposition of iron sulfide gums◦
Usually FeSX formed by reaction of soluble iron compounds (e.g. porphryns) with sulfur in the feed at the top of the hydrotreater
•
Breakage of poor quality bed topping, support media, catalyst or absorbent particles
Specially engineered ceramic materials can greatly alleviate any increase in pressure drop due to these mechanisms.
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Costs of pressure drop rise
•
Cost of reduced catalyst lifetime due to higher pressure operation causing increased hot spots and carbon deposition
•
Cost of extra power required to overcome increased pressure drop
•
Cost of poor product quality caused by reduced selectivity due to operation at higher pressures
•
Cost of reduced catalyst activity due to particulates blocking active sites
•
Cost of skimming operations◦
Cost of replacement catalyst◦
Cost of shut down and start up operations◦
Cost of lost production
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Avoidance of pressure drop increase
Cause of Pressure Drop Increase
Avoidance Measure
Particulate depositionInstall macroporous guard bed material
Iron sulfide gum deposition
Catalyst / absorbent breakageStronger, more robust materials
Bed support breakage
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Deposition of particulates and gums
How does MacroTrap® media work?
How does MacroTrap® media work?
Agenda•
Introduction
•
Causes of pressure drop increase•
Costs of pressure drop rise
•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
MacroTrap® media mitigates pressure drop rise
•
Benefits◦
Macropores to trap particulates
◦
Micropores to enhance subsequent demetallization activity
◦
Micropores also trap smaller particulates◦
Tortuous path improves deposition of particulates and soluble iron
◦
Retain high strength and low attritionMacroTrap Media 1.5
0.46 cc/g1009080706050403020100.001
.01
.1
1
10
100
1000
National Methanol, Ibn Sina, KSA
National Methanol, Ibn Sina, KSA
• Guard bed10mm MacroTrap® media rings (directly on top of the catalyst bed)
Some organic matter was trapped. After firing in air to 1000˚C for three hours◦
Top sample lost 2.1% weight
◦
Bottom sample lost 1.4% weight
Iron is trapped in the pores throughout the body of the MacroTrap® media•
Pilot test - major process licensor◦
750 hours at LHSV 0.5/hr
Intensity
Center
FeAl
Edge
Similar analysis of the top layer of HDM catalyst showed only surface deposition of iron
Electron microprobe analysis across the face of a cut sphere showed iron (and some vanadium and nickel) trapped in the pores
MacroTrap® media has many other applications•
Catalytic reforming and other refinery operations
•
A >99% alumina version is available to remove particulates from steam containing feeds
•
Other service in chemical plants (e.g. methanol, chlorinated hydrocarbons)
•
Natural gas mercury removal•
Proprietary applications
There are over 200 installations worldwide, including many within Sabic, Sipchem and Saudi Aramco (Jeddah refinery).Some guard bed layers are installed as an insurance policy in case of future pressure drop problems.
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Denstone® support media is engineered to perform
•
Particle Packing◦
Particle size distributions optimized to control porosity•
Chemistry◦
Proper raw material selection critical for superior physical performance
◦
Chemistry engineered to maximize matrix strength and chemical resistance
◦
Microstructure◦
Engineered microporosity allows resistance to rapid depressurization and increases thermal shock resistance
•
Manufacturing parameters are carefully controlled ◦
Eliminate flaws ◦
Achieve proper microstructure
Agenda
•
Introduction•
Causes of pressure drop increase
•
Costs of pressure drop rise•
Avoidance of pressure drop increase◦
MacroTrap® guard bed media
An example at Ibn Sina◦
Denstone® bed support media
A new invention◦
Engineered catalyst carriers
◦
Ceramic pentarings•
Compagnie de Saint-Gobain
•
Saint-Gobain NorPro
Total Support Bed Height = 48"
0.0
5.0
10.0
15.0
20.0
25.0
30.0
500 700 900 1100 1300 1500 1700
Mass Velocity, lbs/hr.ft2
Pres
sure
Dro
p (in
ches
wat
er)
Denstone® deltaP™ media pressure drop comparisonTwo layers of Denstone deltaP can replace four or more layers of traditional Denstone spheres, with pressure drop reduced by half.
Spherical Support System (4 layers)
Denstone® deltaP™ Support System (2 layers only)
Denstone® catalyst bed supports - widely used throughout refineries and petrochemical plants