Johnson Matthey - Kevin Mowbray.pdf
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Transcript of Johnson Matthey - Kevin Mowbray.pdf
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Experience in optimizing ATR performance
with high stability KATALCOJM catalysts
Kevin Mowbray
Johnson Matthey
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Introduction
Introduction to autothermal reforming
Catalyst bed fouling and pressure drop build up
Alumina vaporization and transport
High stability reforming catalysts and target tiles
Case study large combined reforming plant
Conclusions
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Autothermal reforming
Increasingly common in methanol plants
Beneficial in larger plants
Alternative feeds such as coke oven gas
Brings several benefits
Low methane slip due to high temperature
Stoichiometric synthesis gas
Improve loop efficiency
Can be employed in several flow schemes
Johnson Matthey have experience designing for all cases
Johnson Matthey have experience with alternative feeds
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Series & combined reforming
Steam
Steam
Steam
Steam
reformer
Oxygen
Natural gas
Autothermal
reformer
Bypass gas
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EMethanex example
3,600mtpd methanol plant
Damietta, Egypt
Combined reforming flow scheme
DPT / Johnson Matthey technology
Johnson Matthey largest autothermal reformer to date
Commissioned Q1 2011
ATR running well
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Autothermal reformer
Alumina lumps or target tiles
Catalyst bed
Refractory
support arch
Alumina lumps
Reformed gas outlet
9501020C
Refractory lining
Oxygen inlet
20250C
Process gas inlet
650750C Burner
~1250C
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Standard catalyst charge
Alumina hold-down lumps or tiles
Guard layer of low activity large pellets
Alumina condenses on large pellets
Minimizes pressure drop build-up
Main bed of standard catalyst
The hold-down material vaporizes
More important than refractory vaporization
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Standard catalyst charge
Alumina lumps or target tiles
Standard catalyst
Alumina lumps
Low activity catalyst
Severely fouled
catalyst forms
in this location
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Target tiles
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Vaporized tiles and large catalyst
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Fouling on main catalyst
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Severe fouling of main bed
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Rubies
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Alumina vaporization
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Effect of condensation
Fouls and blocks the flow paths
Increased pressure drop Reduced rate as reformed gas pressure reduces
Mini shutdowns to skim catalyst bed
Short catalyst lifetime
Loss in activity by physical blinding
Difficulty in discharging catalyst
Fouling of waste heat boiler
Often find rubies Al2O3 contaminated with traces of Cr
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High stability catalyst charge
Hold down tiles or lumps (KATALCOJM 94-1)
high density stabilized ceramic
reduces vaporization from tiles by >90%
guard bed of high activity (KATALCOJM 89-6Q)
refractory metal on a stabilized ceramic
cools gas rapidly below vaporization temperature
main bed of KATALCOJM 28-4Q
reduces vaporization and pressure drop
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KATALCOJM 94-1 and 89-6EQ
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Case study
Large combined reforming based methanol plant
1997 2007 ran with alumina based catalysts in ATR
Experienced pressure drop build-up
Bed needed skimming at each maintenance turn around
Installed JM high stability catalysts in 2007
Very low rate of pressure drop rise
Catalysts removed and reloaded due to refractory repair in 2010
Operated through till a planned changed out on 2014
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KATALCOJM 89-6 charge in July 2007
KATALCOJM 94-1 tiles
KATALCOJM 28-4Q catalyst
KATALCOJM 94-1 lumps
KATALCOJM 89-6GQ catalyst
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KATALCOJM 89-6 charge in July 2007
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Pressure drop 0 3 years
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Overhaul July 2010
Internal inspection in September 2009 identified problems with the refractory lining
Major repairs planned for July 2010
3 years after KATALCOJM 94-1 and 89-6 was installed
Pressure drop had built up by only a small amount
Tiles and catalyst in as new condition during inspection
Decision made to remove the catalyst and recharge
Some spare catalyst ordered to make up for breakage
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KATALCOJM 94-1 tiles
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KATALCOJM 94-1 lumps
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KATALCOJM 89-6GQ catalyst
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KATALCOJM 28-4Q catalyst - top
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Findings after 3 years service
KATALCOJM 94-1 tiles and lumps in excellent condition
Small number of tiles with some cracks but reusable
Carefully removed and reused
KATALCOJM 89-6GQ catalyst in excellent condition
Small number of broken pellets but OK for reuse
There was no alumina condensed on the 89-6GQ
This remained in as new condition
KATALCOJM 28-4Q catalyst in good condition
Very top of bed slightly fouled with alumina
Replaced with KATALCOJM 28-4EQ catalyst Larger holes so less easy to foul in the future
Rest of bed in excellent condition and reused
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KATALCOJM 89-6 charge in July 2010
KATALCOJM 94-1 tiles
KATALCOJM 28-4Q catalyst
KATALCOJM 94-1 lumps
KATALCOJM 89-6GQ catalyst
KATALCOJM 28-4EQ catalyst
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Pressure drop 0 6 years
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Findings after 6 years service
KATALCOJM 94-1 tiles and lumps in excellent condition
Minor spalling, no evaporation, no discolouring
Described as good as new
KATALCOJM 89-6GQ catalyst in excellent condition
No sign of vaporization
No ruby formation
Some pellet breakage observed
KATALCOJM 28-4Q catalyst
Only very top of bed inspected
Vaporization of pellets seen in mixed layer of KATALCOJM 89-6GQ and KATALCOJM 28-4Q from 2010 reload
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ATR inspection June 2013
KATALCOJM 94-1 Tiles
Top of bed
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ATR inspection June 2013
KATALCOJM 89-6GQ and KATALCOJM 94-1 lumps
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Operation through till end of run
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Findings after 7 years service
KATALCOJM 94-1 tiles and lumps in excellent condition
Minor spalling, no evaporation, no discolouring
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Findings after 7 years service
KATALCOJM 89-6GQ catalyst in excellent condition
No sign of vaporization
No ruby formation
Some pellet breakage observed
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Findings after 7 years service
KATALCOJM 28-4Q catalyst
Vaporization of pellets seen in mixed layer of KATALCOJM 89-6GQ and KATALCOJM 28-4Q from
2010 reload
alumina based supports are not as thermally stable as high density stabilized ceramics
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Conclusions
Johnson Matthey have extensive experience in the technology of autothermal reforming
Johnson Matthey have demonstrated a range of superior target tiles and catalysts for autothermal reformers
These catalysts operated successfully with less pressure drop build-up for 7 years in a large combined reforming
methanol plant
Johnson Matthey catalysts and inert materials loaded again in 2014.