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*Email: chris.murkin@matthey.com
Organic Sulfur
Furnace con and
version removal Part
desulfurised
feedstock gas
Make gas HP steam
WH boiler
Reaction steam superheater
Flue gas
WH boiler
CO Gas
Reaction gas
converter
Burner air boosters
preheater
preheater
Product
gas
Fig. 3. The methane-steam plant owsheet from Billingham 1936 (Reproduced with permission from (2))
Rapid Technical Developments gas supply was interrupted the plants were congured
to switch feedstock online to a liqueed petroleum gas
With reformer temperatures and pressures rising (LPG) stream (which was stored locally in underground
with advancing tube metallurgy, silica migration salt caverns), bringing a demand for catalysts that
was becoming increasingly problematic. So in the could cope with feedstock exibility. This brought new
mid-1950s a low silica product was produced. ICI requirements for a catalyst with lower potash and
catalyst 57-1 contained less than 0.2% Si, but was still higher activity in order to optimise the reformer for
made using the precipitated catalyst route. this feedstock. By the end of the decade there were
As naphtha feeds were shown to be more economic two light potash catalysts KATALCOJMTM 25-3 (1.6%
than methane sourced from coke gasication, ICI potassium oxide (K2O)) for natural gas feeds and
started an extensive research programme to develop a KATALCOJMTM 46-9 (2.2% K2O) for LPG feeds (5). By
catalyst which could efciently reform naphtha (1). They the end of the 1970s, KATALCOJMTM had a product
discovered alkalis as a useful promoter for the catalyst, range very similar to the present: KATALCOJMTM
with potash being the most effective. Alkali addition 57-series non potash, KATALCOJMTM 25-series light
benets the catalyst by neutralising the support acidity potash and KATALCOJMTM 46-series naphtha catalyst.
retarding carbon forming reactions and increasing By this point the catalyst beds were operating at
the rate of carbon removal (1). Commercially this was temperatures up to 1000C and 35 bar pressure,
launched as ICI catalyst 46-1 and enabled ICI in 1959 primarily due to improvements in metallurgy (4).
to design the rst naphtha reforming plant. This was
built in Heysham, UK, and was commissioned in 1962. Steam Reformer Design
This was deemed a success and was soon followed
by four new plants in Billingham. These plants were A paper by Davy Powergas Ltd in the early 1970s
operating at moderate pressures of 14 bar at the inlet, (6) suggested that LPG transportation would not
a sign of metallurgical progress. be cost effective and instead huge methanol plants
In the late 1960s the KATALCOJMTM brand was (25,000 (metric) tonnes per day (TPD)) would produce
launched as ICI began to sell catalysts externally and fuel grade methanol to be shipped around the world.
became signicantly more active in attending external They predicted a 5000 TPD plant would require a 2000
conferences and marketing the catalyst (3). tube reformer, a huge increase over the largest at the
Towards the end of the decade, ICI developed a time (600 tube reformer for Celenese Chemicals Co,
catalyst made by impregnating a red refractory USA). Whilst the benets of hindsight show that these
support using a metal salt solution to produce a well predictions were somewhat optimistic especially about
distributed surface layer of nickel. This was launched methanol as a fuel, they correctly predicted 5000 TPD
as KATALCOJMTM 57-3 and had the main advantage methanol plants which we have now. Modern plants
of being much stronger mechanically than previous require fewer than half the tubes suggested at the
catalysts. Early low silica precipitated catalysts time an indicator of progress in tube materials and
lost 50% of their strength after reduction, whereas catalysts. Prognosticating accurately, they suggested
KATALCOJMTM 57-3 retained over 80% strength even the construction of modular top red reformers, which
after four years in service (4). Pellets could also be enabled high tube count reformers without being
made smaller, something not possible with precipitated prohibitively long (Figure 4). They suggested features
catalyst, which gave process engineers the option to such as combustion air preheating and an induced
choose between high activity or lower pressure drop draft convection section in order to improve efciency,
options. which are all commonly found on todays plants.
In 2006 Johnson Matthey acquired Davy Process
Cheap North Sea Gas Technology, who by then had seen the commissioning
of M-5000 in Trinidad, the worlds largest steam
In the 1970s, Billingham ammonia plants changed from reformer-based methanol plant operating at 5400 TPD.
naphtha feeds to run on the newly commercialised The development of reformer tube metallurgy has
natural gas from the North Sea, however the favourable been shown to be a key enabler in the development
gas contract was on an interruptible supply basis of steam reforming. All steam reformer tube alloys are
meaning that with short notice the feedstock could be centrifugally cast from steels with high carbon content,
cut when demand for natural gas was high. If natural plus around 25% chrome, 2035% nickel and some
99 20
HK-40
Feedstock Inlet
header pigtail
IN-519
15
Minimum thickness, mm
HP-Mod Nb
Section through Reformer
furnace showing tubes
HP microalloy
one module
10
Cofn
5
Reformed gas
outlet
Outlet pigtail
Ports for removing
products of combustion 0
Collecting duct Tube material
Fig. 5. Comparison of HK-40 15.5 mm, HP-modied
One
module Burners Tubes
Fig. 6. Evolution of catalyst shapes with time and comparison of their properties (10) (Adapted with permission from
International Fertiliser Society Proceedings)
11. B. J. Cromarty, The Development and Application of 16. F. Lynch, Johnson Matthey: The New Force
Shaped Primary Reforming Catalyst, ICI Catalysts in Catalysis, Fertilizer Focus, January/February
Customer Symposium, Thaicat 90, Bangkok, Thailand, 2004, p. 49
May, 1990, ICI Katalco Technical Papers
12. B. J. Cromarty, Nitrogen, 1991, 91, 115
Further Reading
13. W. J. Cotton and M. P. Roberts, Application and
Operation of the Quadralobe Steam Reforming J. Brightling and J. Pach, Ammonia Production A Century
Catalyst Shape in Methanol Plants, International of Safety, Health & Environmental Improvements,
Methanol Technology Operators Forum (IMTOF), 58th Annual Safety in Ammonia Plants and Related
London, UK, 2003 Facilities Symposium, Frankfurt, Germany, 25th29th
14. W. Whittenberger and P. W. Farnell, Foil Supported August, 2013
Catalysts Deliver High Performance in Steam J. Phillips, A Short History of ICI at Billingham The First
Reformers, International Methanol Technology 60 Years 19171977 Billingham, 1986
Operators Forum (IMTOF), London, UK, 7th10th W. Whittenberger and P. Farnell, Foil Supported
June, 2015 Catalysts Deliver High Performance in Steam
15. M. P. U. Carlsson, J. G. Oliver, M. R. Feaviour, D. Reformers, Nitrogen + Syngas 2015 28th
J. Birdsall and S. A. French, Johnson Matthey Plc, International Conference & Exhibition, Istanbul,
Catalyst Preparation Method, European Patent Turkey, 23rd26th February, 2015, Proceedings of
2,424,657; 2012 Nitrogen + Syngas 2015, p. 21
The Authors
Chris Murkin is a Graduate Process Engineer at Johnson Matthey Process Technologies,
Chilton, UK. He obtained his MEng in chemical engineering from the University of Cambridge,
UK. On the graduate training scheme, he has spent a year on the catalyst manufacturing site in
Clitheroe, UK, and is coming to the end of his second placement considering steam reforming
applications and design tools.