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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, Dhahran
16 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Graded beds have been replaced by more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
The old way

Graded Denstone
support media

Feed

Feed

The new way


Pentaring bed
topping media
MacroTrap media
HSA alumina ring

Main catalyst
(supplied by
others)

Main catalyst
(supplied by
others)

Denstone
support media

Denstone deltaP
support 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

Avoidance

Drop Increase

Measure

Particulate deposition
Install macroporous guard bed
material
Iron sulfide gum deposition
Catalyst / absorbent breakage
Stronger, 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 attrition
MacroTrap Media 1.5
0.46 cc/g

100
90
80
70
60
50
40
30
20
10
0
.001

.01

.1

10

100

1000

National Methanol, Ibn Sina, KSA

National Methanol, Ibn Sina, KSA


Feed
Natural gas
390C
30 bar
Flow 83,000Nm3/hr
Velocity 0.26m/sec

Composition
C1/C2 = 75 / 25%
C4, C5 up to 1%
6 10ppm sulfur
compounds

Contaminants
Rust (tramp iron)
Carbon dust
Heavy hydrocarbons

Guard bed
10mm MacroTrap media
rings (directly on top of the
catalyst bed)

Catalyst
Commercial
hydrodesulfurization
catalyst

National Methanol, Ibn Sina, KSA


The National Methanol (Sabic) desulfurizer has run for
73 months with no significant increase in pressure drop

National Methanol, Ibn Sina, KSA


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

7X magnification

National Methanol, Ibn Sina, KSA


Some organic matter was trapped. After firing in
air to 1000C for three hours
Top sample lost 2.1% weight
Bottom sample lost 1.4% weight
XRF testing showed iron pickup
Sample

2008670062

2008670063

2008670076

Location
Al203

Top of Layer
93

Bottom of Layer
94

Unused Rings
97

CaO
Fe2O3
K2O
SiO2
TiO2

0.1
3.6
0.1
2.8
0.1

0.1
2.8
0.1
2.8
0.1

0.1
0.1
0.1
2.8
0.1

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

Electron microprobe analysis


across the face of a cut sphere
showed iron (and some vanadium
and nickel) trapped in the pores

Intensity

Fe
Al

Edge

Center

Similar analysis of the top layer


of HDM catalyst showed only
surface deposition of iron

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

Denstone deltaP media


pressure drop comparison
Two layers of Denstone deltaP can replace four or more
layers of traditional Denstone spheres, with pressure
drop reduced by half.
Total Support Bed Height = 48"

Pressure Drop (inches water)

30.0
25.0
20.0
15.0

Spherical Support System


(4 layers)
Denstone deltaP Support
System (2 layers only)

10.0
5.0
0.0
500

700

900

1100

1300

Mass Velocity, lbs/hr.ft2

1500

1700

Denstone catalyst bed supports - widely


used throughout refineries and
petrochemical plants
Process

Preferred Denstone
Brand Ceramic
Support Media

Process

Petroleum Refining
Hydrocracking

2000 / deltaP

Hydrotreating

Preferred Denstone
Brand Ceramic
Support Media
Ammonia Plants

Desulfurizers

99 / deltaP

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

Methanator

99 / deltaP

Isomerization
Claus Reactors

57 / deltaP

Natural Gas Processing

57 / 2000 / deltaP

Petrochemical

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

Desulfurizers

57 / 2000 / deltaP

Molecular Sieve

57 / 2000 / deltaP

Separations

99 / deltaP

Polymerization

99 / deltaP

Acid Plants
Separations

57 / 2000 / deltaP

Industrial Gases
Dryers

57 / 2000 / 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
Low cost,
low activity,
non-porous
ceramic
formulation
Sizes
available

55 lb/ft3 / 885
kg/m3
Non-reactive
composition

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
Example of a Gas Oil Hydrotreater
(13.5 foot diameter)
Pentaring Bed Topping Media .5
MacroTrap Media 1.5

Cost

% of Total
Cost

$6,494

0.4%

$61,341

3.9%

5.0%
Main Catalyst - 54

Denstone Support Media 2.0

$1,495,646

95.0%

$11,052

0.7%

$1,574,543 Total 100%

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

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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

Catalytic Products
Proppants
Process Ceramics

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headquartered in Stow, Ohio
Steinefrenz,Germany
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