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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Graded beds have been replaced by more advanced systems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)
• CatalystCommercial hydrodesulfurization catalyst
FeedNatural gas390°C30 barFlow – 83,000Nm3/hrVelocity – 0.26m/sec
CompositionC1 /C2 = 75 / 25%C4 , C5 – up to 1%6 – 10ppm sulfur compounds
ContaminantsRust (“tramp iron”)Carbon dustHeavy hydrocarbons
National Methanol, Ibn Sina, KSAThe National Methanol (Sabic) desulfurizer has run for 73 months with no significant increase in pressure drop
National Methanol, Ibn Sina, KSA
7X magnification
Two samples were retrieved from the reactor at changeout – one from the top of the MacroTrap® media bed and one from the bottom of the bed
SampleLocation
2008670062Top of Layer
2008670063Bottom of Layer
2008670076Unused Rings
Al2 03 93 94 97CaO 0.1 0.1 0.1
Fe2 O3 3.6 2.8 0.1K2 O 0.1 0.1 0.1SiO2 2.8 2.8 2.8TiO2 0.1 0.1 0.1
XRF testing showed iron pickup
National Methanol, Ibn Sina, KSA•
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
ProcessPreferred Denstone®
Brand Ceramic Support Media
ProcessPreferred Denstone®
Brand Ceramic Support Media
Petroleum Refining Ammonia PlantsHydrocracking 2000 / deltaP™ Desulfurizers 99 / deltaP™
Hydrotreating 57 / 2000 / deltaP™ Secondary Reformers 99 / deltaP™
Hydrogenation 57 / 2000 / deltaP™ Low-Temperature Shift 99 / deltaP™
Reforming 57 / 2000 / deltaP™ High-Temperature Shift 99 / deltaP™
Isomerization 57 / deltaP™ Methanator 99 / deltaP™
Claus Reactors 57 / 2000 / deltaP™ Natural Gas ProcessingPetrochemical Dryers 2000 / 57 / deltaP™
Hydrocracking 57 / 2000 / deltaP™ LPG Treaters 57 / 2000 / deltaP™
Hydrotreating 57 / 2000 / deltaP™ LNG Prepurifiers 57 / 2000 / deltaP™
Oxidation 57 / 2000 / deltaP™ Claus Reactors 57 / 2000 / deltaP™
Absorbers 57 / 2000 / deltaP™ Acid PlantsDesulfurizers 57 / 2000 / deltaP™ Separations 57 / 2000 / deltaP™
Molecular Sieve 57 / 2000 / deltaP™ Industrial GasesSeparations 99 / deltaP™ Dryers 57 / 2000 / deltaP™
Polymerization 99 / deltaP™
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
Catalyst carrier requirements must insure long life in the reactor
•
Proper porosity (water absorption)
•
Adequate strength•
Low abrasion
•
Sufficient surface area•
Controlled chemistry
•
Consistency
Saint-Gobain NorPro has been engineering high performance catalyst carriers for well over 60 years
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
Ceramic pentarings, low pressure drop
High void fraction of 62%
rings 52%spheres 40%
Dense media for efficient hold-down
55 lb/ft3 / 885 kg/m3
Low cost, low activity, non-porous ceramic formulation
Non-reactive composition
Sizes available
10mm (3/8”)13mm (1/2”)19mm (3/4”)25mm (1”)
Why ceramic materials are useful
•
High attrition resistance•
Strength and creep resistance at high temperatures
•
Corrosion resistance•
Resistance to oxidation
•
Optimized non-reactive compositions•
Moderate cost
Saint-Gobain NorPro offers a high return for a low investment
Pentaring Bed Topping Media – .5’
Example of a Gas Oil Hydrotreater(13.5’ foot diameter)
MacroTrap® Media – 1.5’
Main Catalyst - 54’
Denstone® Support Media – 2.0’
Cost
$6,494
$61,341
$1,495,646
$11,052
$1,574,543
% of Total Cost
0.4%
3.9%
95.0%
0.7%
100%Total
5.0%
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
Compagnie de Saint-Gobain, a world leader in engineered materials
ConstructionProducts$16.4BN
High Performance MaterialsSales $7.0BN30,000 employeesOver 265 manufacturing facilities in 37 countries
Building Distribution$28.8BN
Flat Glass$8.3BN
Packaging$5.2BN2007 Sales:
€43.4BN; $64.2BN
>200,000 employees
North America Sales$8.6BN
Grains & Powders
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Textile solutions
Abrasives
High Performance Materials – Six main families of activities
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
Saint-Gobain NorPro
“Technology driven ceramic solutions for hydrocarbon processing industries”
ProppantsCatalytic Products
Process Ceramics
Saint-Gobain NorPro, globally located headquartered in Stow, Ohio
Plant
Plant and Sales Office
Sales Office
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HQ
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