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AIChE honours Anders Nielsen

Summary

The annual Safety in Ammonia Plants Symposium took place this year in Tucson, Arizona. Dr Anders Nielsen, doyen of ammonia process experts and long-time associate of Haldor Topsøe, received the Ammonia Safety Committee's distinguished service award.

Abstract

For its 45th meeting the American Institute of Chemical Engineers’ “Safety in Ammonia Plants and Related Facilities” Symposium returned to the Loews Ventana Canyon Resort outside Tucson, Arizona - the same location as five years ago. Outside temperatures reached a heady 107ºF (42ºC) during the course of the meeting - very unusual for September - but on account of the dry desert air it was bearable outdoors out of the direct sunlight. Sadly but unsurprisingly, given the invidious trading circumstances of the US nitrogen industry, numbers were a bit down this year, but as always the sessions were well attended by an attentive and interested audience.

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The long and winding road

Summary

For the past few years, the methanol industry has been tantalised by the prospect of greater demand for its product via methanol-based fuel cells, primarily in cars. Nitrogen & Methanol assesses the current state of commercialisation of fuel cell vehicles and the prospects for methanol.

Abstract

The technology of fuel cells has already been extensively discussed in previous articles (Nitrogen 230, Nov/Dec 1997, Nitrogen & Methanol 242, Nov/Dec 1999). This article aims mainly to consider the market questions: when or if methanol fuel cells will be introduced, and how much methanol will be required?

Fundamentally, fuel cells require hydrogen and oxygen as a fuel. Oxygen is readily available from the atmosphere – the question is basically from where to source hydrogen. Fuel cells are not a new phenomenon – they are essentially reverse electrolysis, and have been known since 1839. Previous lab-scale fuel cell research has generally used pure hydrogen, and so it is not surprising that fuel cells using pure hydrogen are furthest down the line in terms of research and development.

However, hydrogen is a difficult substance to handle: it is a gas and so, if not generated on-board, must be stored either compressed or cryogenically cooled. For this reason, people have looked to liquid fuels for mobile – especially passenger vehicle – applications, from which hydrogen can be generated ‘on the spot’. It is possible to store hydrogen as metal hydrides, and Shell amongst others has been examining this technology, but metal hydride storage is heavy, which could limit its application to passenger cars. Shell’s collaboration with hydride specialist ECD ended recently after 12 months with neither partner willing to continue together.

Methanol is therefore a strong contender as a fuel for vehicle-based fuel cell operations. It has a lower hydrogen to carbon ratio than gasoline, and due to the lack of carbon-carbon bonds, can be reformed to hydrogen at much lower temperatures than other organic compounds: 250–300C, as opposed to 800–900C for gasoline reforming. The methanol reforming process is also more efficient and better known – more work has been done on it. On-board reforming has its disadvantages; vehicle design becomes more complex and challenging, and the reformer frequently has a long ‘warm-up time’ – in the order of several minutes. For this reason a series of ‘hybrid’ vehicles have been under development using battery power for the first few minutes of travel until the reformer is up to temperature.

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Markets for methanol

Summary

Nitrogen & Methanol takes a look at the main derivatives of methanol, and how demand is projected to shape up in the future.

Abstract

Methanol is used in a wide variety of applications, from direct blending as a solvent or gasoline additive, a component of anti-freeze, synthetic protein production, and chemical synthesis in a variety of end-uses, such as dimethyl terephthalate (DMT), t-amyl butyl ether (TAME) and methyl methacrylate. However, somewhere around 70% of global demand is occupied with just three major derivative chemicals: acetic acid, formaldehyde, and methyl t-butyl ether (MTBE). Accordingly, it is upon those three major derivatives that this article will focus.

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What's going on in methanol synthesis?

Summary

There's already talk of 10,000-t/d methanol plants, but process and catalyst designers are getting abreast of it.

Abstract

Superficially, the “front end” of a methanol plant bears a striking resemblance to that of an ammonia plant. Indeed, it is possible to design a plant that can produce either or both products according to the conditions in their respective markets, although on account of the substantial capital cost of such an arrangement it has not hitherto been widely put into practice.

Hydrocarbon feedstock (nearly always natural gas these days) is preheated, hydrogenated over cobalt-molybdenum catalyst to convert traces of organic sulphur compounds into hydrogen sulphide and then passed through a zinc oxide bed to remove hydrogen sulphide to a very low level, mixed with medium-pressure steam, reheated, and then passed through vertical tubes filled with nickel-based catalyst in a furnace. Here the highly endothermic steam reforming reaction takes place, in which the methane and steam are converted to carbon monoxide, carbon dioxide and hydrogen.

CH4 + H2O <-> CO + 3H2

CO + H2O <-> CO2 + H2

In an alternative to this conventional process concept, the steam reformer is a large heat exchanger which recovers high-level heat from the reformed gas to drive the reforming reaction. However, the energy balance is inadequate without additional oxygen, and the concept has not yet been scaled up to the extent that it can replace the conventional reforming furnace in the very large-scale plants of today.

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Methanex's legal battle

Summary

Following the decision by governor Davis of California to mandate a phased ban on MTBE within the state, Methanex launched a legal challenge under the North American Free Trade Agreement (NAFTA). This article summarises the current situation.

Abstract

On March 25th 1999, governor Gray Davis of California signed an Executive Order stating that “on balance, there is significant risk to the environment from using methyl tert-butyl ether (MTBE) in gasoline in California”, and approving the removal of MTBE from all gasoline in the state, with a three year phase-out to be completed by December 31st, 2002. The Californian Senate has ratified the governor’s decision, and the California Air Resources Board (CARB) has issued new gasoline specifications beginning in 2003 which prohibit the use of MTBE. Part of the Executive Order also asks Federal government to waive the oxygen mandate in reformulate gasoline. The winter oxygenate mandate is to be reviewed, but in any event MTBE will not be allowed as an oxygenate after 2002.

Since MTBE is used almost exclusively as a gasoline additive, the Order looked to be the death knell for the US MTBE industry, and with it a large slice of the US – and global – methanol market.

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Focus on Rotterdam

Summary

With methanol production increasingly moving to remote low-cost gas locations, a key determinant in the profitability of producers has become transport costs. Nitrogen & Methanol looks at Rotterdam, now established as the key landing site for methanol in Europe, and talks to newly-merged Vopak, the largest handlers of methanol in Rotterdam.

Abstract

Since the mid-1980s, there has been a significant change in the way that the methanol market has worked. Long-established production sites near to customers in the industrialised world have begun to lose market share to remote producers. Gas economics have been the driving force: as gas markets have become more integrated, and gas-powered electricity production has expanded, so gas producers have found that they can achieve higher prices for their gas by selling to power producers, and gas-based chemical producers in Europe and North America have been squeezed.

Because methanol can be transported relatively easily, the methanol industry has begun to cast about for cheaper locations around the world where methanol can be produced, from gas which cannot realistically be used for power production and so which remains relatively cheap. Methanex have led the trend with their huge complex at Punta Arenas in Chile, but Saudi Arabia, New Zealand and Trinidad have all become established as major methanol production hubs, and they have been joined more recently by Statoil in Norway, and as of next year Equatorial Guinea.

It is expected that the European methanol market will start to see increasing competition as suppliers from these remote locations vie for European market share with established producers within Europe.

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