Zeolites and World Markets.

Given that the current world production of zeolites amounts to around 4 million tonnes annually, a resource that shows no sign of running-out, it is of interest to predict how this market may behave , say to 2010. As I have noted "Zeolites - La Roca Magica" and "Zeolites - the Stones that Boil", these are unique materials with many highly important applications, particularly in environmental chemistry. They are hydrated aluminosilicates consisting of a negatively charged framework of micropores of molecular dimensions (usually less than 13 A in size) whose charge is balanced by sufficient positively charged cations to provide an overall electrical neutrality. In naturally occurring zeolites, the cations are mostly of the alkali and alkaline earth metals, respectively sodium and potassium and calcium and magnesium. The first mineral to be classified as a zeolite was discovered in 1756, since when about 48 natural zeolite types have been identified.
The most common natural zeolites are analcime, chabazite, clinoptilolite, heulandite (there is some speculation as to whether heulandite and clinoptilolite should simply be classified as one mineral), laumontite, phillipsite, ferrierite and erionite (which due to its fibrous nature and high iron content is a Class 1 carcinogen). Overwhelmingly, clinoptilolite is the major zeolite used for commercial applications, while chabazite and mordenite are used on a lesser scale. In an effort to exploit its extensive deposits in the United States, laumontite has come into focus as a potential commercial product. A further 150 zeolites have been artificially synthesised, the first of which was made in 1949 in the Linde division of the Union Carbide Corporation in the U.S. (Linde A, or zeolite A), and the most commercially important are zeolites A, X, Y and ZSM-5.
The natural zeolites have not gained the commercial niche-market of the synthetic forms, mainly because of limitations in availability (need to import), large variations in mineral composition (synthetic zeolites are more uniform in composition, don't need to be extracted from surrounding tuffaceous rock "tuff", clay and limestone etc), crystal size (synthetic zeolites are more uniform in this respect too, although the grains of them tend to be larger than those of their natural counterparts), porosity and pore diameter. Synthetic zeolites are generally constructed around an organic "template" which defines the above properties more precisely than nature does.
Nonetheless, natural zeolites are used on a huge scale for more low-tech applications, particularly in environmental clean-up operations, cat-litter, animal feed, fertilisers, aquaculture (fish farming), soil amendment, radioactive decontamination, industrial water softeners, heavy metal removal, heat storage, solar refrigeration and pollution control and overwhelmingly for use in light-weight cement: mostly in China, which uses 2.5 million out of the annual 4 million tonnes mined globally for this particular purpose.
The largest market for synthetic zeolite is as a water softener "builder" in detergents. As an alternative to "phosphates"which were found to cause algal blooms in lakes, around 1.3 million tonnes of zeolite A is used annually. The traditional sodium tripolyphosphate has been banned on environmental grounds, although the problem of algal bloom is not entirely eliminated since most of the "phosphate" originates from human activities, including agricultural use of "phosphate" fertilisers. With market saturation and production overcapacity in the regions of the "Industrial Triad" the potential growth market for zeolites is in the Asia-pacific region. Synthetic zeolites are also used on a large scale in the petrochemical industry for catalytic "cracking" (an inherently "green(ish)" process since it enables the production of specific product fractions from oil, specialty chemical feedstocks (e.g. para-xylene for the polyester textile industry) using less energy than would be the case without them.
There are environmental drivers to reformulate gasoline and to reduce sulphur emissions which have provided a boon to the zeolite market. The catalytic activities and selective nature of zeolites can be tuned to a considerable degree by modifying both the zeolite framework and the cations it contains. Average levels of zeolites in fluid catalytic cracking (FCC) catalysts have risen in general and ZSM-5 is now used increasingly in such catalytic composites to increase olefin (alkene) production. In terms of product selectivity, zeolites show overwhelming advantages over the more traditional Lewis Acid catalysts such as aluminium chloride and phosphoric acid based materials. Although such zeolite catalysts are used on a scale of around 117,000 tonnes annually, i.e. less than one tenth that used in detergents, the value basis is around 55% of the global market.
In the future, a greater volume is expected for the automobile industry, since by the use of zeolites in catalytic converters, the more fuel-efficient "lean burn engine" can still be used but still keeping such empowered vehicles within projected emissions targets. The lean burn engine is efficient because it runs at a higher temperature than normal and converts more of the fuel to miles on the road. However, the higher temperature also tends to "fix", combine nitrogen and oxygen , thus pumping out more NOx pollution, which the metal-loaded zeolite catalyst is able to decompose before it can escape and cause problems.
The global market for natural zeolites is expected to grow from 3.98 million tonnes to 5.5 million tonnes by 2010. In the same time period, the consumption of synthetic zeolites is projected to amount to 1.86 million tonnes. The value of the combined market would then amount to $3 billion (and that is excluding the total value of the products themselves whose production depends on zeolites).
It all looks very rosy, and one might be tempted to make extrapolative projections into the future. The only problem is that the entire zeolite industry: extraction or synthesis, and the source of chemical feedstocks for the range of industries in which they are involved (including food production using chemical fertilisers) depends on oil either at some stage or directly or both. Such economic predictions are surely only valid so long as cheap oil is available, or else a completely alternative picture might emerge. Economists and industrialists, and all of us for that matter, should not be rhetorically swept away from the imminent reality that is "Peak Oil".

Chernobyl - How many Really will Die?

In reflecting upon the aftermath of the world's most devastating nuclear disaster, which happened at the Chernobyl nuclear power station 20 years ago in the early hours of 26 April, it is noteworthy to find that consensus has yet to be met on precise numbers of its victims.
The Chernobyl disaster occurred at 01:23 a.m. on 26 April, 1986 at the Chernobyl nuclear power plant in Pripiat, Ukraine. Because there was no containment building, a plume of radioactive fallout drifted over large areas of the former U.S.S.R., western Europe and the eastern United States. In the U.S.S.R., Ukraine, Belarus and Russia were badly contaminated, resulting in the evacuation and resettlement of over 336,000 people. Official post-Soviet data indicates that about 60% of the radioactive fallout landed in Belarus. According to the 2006 TORCH report, the disaster released more than 300 times the radioactive fallout from the atomic bombs dropped on Hiroshima and Nagasaki, half of which landed outside the three Soviet republics: in total 34% of the Earth's surface was contaminated by it.
The countries of Russia, Ukraine, and Belarus, now independent, have been burdened with continuing and substantial decontamination and health care costs. Soviet-era secrecy has obfuscated arriving at an accurate figure for the number of deaths, for example Soviet authorities forbade doctors to cite "radiation" as a cause of death; presumably some other cause e.g. "pneumonia" was instead ascribed on death certificates in such cases. Most of the expected cancer deaths have yet to occur, and will be difficult to attribute specifically to the accident.
A 2005 report (Chernobyl Forum), led by the International Atomic Energy Agency (IAEA) and World health organisation (WHO), concludes that 56 direct deaths are a result of the immediate events at Chernobyl. This is the sum of 47 "liquidators" - those sent in immediately to stabilise the blazing reactor and the 9 children who are known to have died from thyroid cancer as a result of ingesting radioactive iodine from the radioactive plume. They estimate that up to 9000 people, of the more than 6 million most heavily exposed to radiation from Chernobyl will die from some form of cancer as a consequence.
Greenpeace, however, has challenged these figures in a new report. Based on research at the Belarus National Academy of Sciences, the Greenpeace report concludes that worldwide 2 billion people have been affected by the fallout from Chernobyl and that 270,000 of them will develop cancer as a consequence of this, of which 93,000 will prove fatal. In contrast, the Chernobyl Forum, which is a group of 8 U.N. agencies along with the governments of those most heavily contaminated countries Ukraine, Belarus and Russia, is adamant that the toll is in the thousands only (not that this is insignificant!).
Gregory Haertl, a spokesman for the Geneva-based WHO said the organisation stood by its figures of 9000, while Greenpeace anti-nuclear campaigner Ivan Blokov has accused the IAEA of "whitewashing the impacts of the most serious nuclear accident in human history".
As I noted in my previous posting "Chernobyl (26th April 2006); 20 Years On" it is not only the deaths that occurred directly or even those that may subsequently be attributed to the consequences of the Chernobyl disaster itself, e.g. cancer and other diseases of radiation exposure in relation to those who were thereby contaminated. The decline in social conditions, fragmentation of communities and a pervading spirit of despair has undoubtedly contributed to unhealthy lifestyle changes (e.g. cigarettes and vodka) amid the cloud of thinking that Chernobyl will "get you" or your children in the end, and the future is dark and hopeless. This may well have led to many more deaths or will do than Chernobyl did alone.
Official estimates from Ukraine, Belarus and Russia are that around 25,000 people died by 2005 , but 20 years on, many of the "survivors'" descendents are still suffering the effects of the nuclear fallout. There are problems (also noted in nuclear workers - men) that radiation exposure of a parent who remains apparently healthy may show-up as birth defects in their children. Out of the 3 million people that the Ukrainian government recognise as victims of Chernobyl, 642,000 are children, and many of this population continue to live in the vicinity of the moth-balled power station, despite the fact that the soil and water are heavily radioactively contaminated for 30 km around.
Chernobyl's last functioning reactor was shut down in December 2000, and the 3500 people who still work there are mainly involved in maintaining the giant concrete sarcophagus used to contain further emissions of radiation. The initial shell was installed fairly rapidly, but over the years huge steel girders have been installed in order to prop up the foundations and external walls of the sarcophagus. It is thought that presently the sarcophagus is in a "satisfactory condition" but that it must be further stabilised before a second and stronger wall, nicknamed "The Arch" can be built. The 190 metre wide and 200 metre long "Arch" will be made in the shape of a half-cylinder and will literally slide over the existing sarcophagus: I presume thereby providing containment even in the event that the latter does finally collapse as has been feared practically since its construction, as it was - and had to be, given the prevailing circumstances - put up in a rapid and perhaps shoddy manner. The steel structure of the Arch will weigh in at more than 18000 tonnes - more than twice the steel used to make the Eiffel Tower.
As far as future emissions from Chernobyl are concerned, let's hope that is the end of it, but either way, the human legacy looks set as a perennial problem.

Bargain Nuclear Waste Disposal and China Nuclear Power.

It seems that the massive £70 billion cost of cleaning-up 20 of the U.K.'s civil nuclear sites, Sellafield being the largest, could be cut by up to 25% (£17.5 billion) if British Nuclear Group (BNG) is bought up by Washington Group, which controls a third of the U.S. nuclear remediation market. It is expected that the U.K. decommissioning programme could generate £2 billion a year, a lucrative amount, considering the initial outlay of somewhere between £250 million and £1 billion needed to buy up BNG, which is effectively "state-owned" and is a company with contracts to operate nuclear sites within the U.K., including Sellafield.
The government wants to privatise BNG, which is a part of British Nuclear Fuels Ltd., by the end of 2007. Bidders will be chosen later this year, and then invited to submit tenders in the spring of 2007. The process will be a tough contest, and Washington will have to compete against other potential buyers with clout, incuding other "Americans", Bechtel and CH2M Hill and the U.K.'s own Amec.
Washington has the contract to clean-up the Savannah River Site in South Carolina, and claims that it has saved the U.S. government $16 billion (around £9 billion) - also about a quarter of the original estimate, so this presumably is the basis of the competitive deal offered to the U.K.? - and that the timescale for its decommissioning has been reduced by 23 years.
Some are sceptical that such an apparent bargain might apply in the U.K., on the basis that the huge savings made in the U.S. stem largely from reducing the scope of the clean-up operations, which sounds almost like a suggestion of "cutting-corners". Washington challenge this criticism insisting that they have made their savings through greater operating efficiency and better use of facilities. One example they give is that they have saved $450 million by converting an old reactor at Savannah River into a plutonium storage facility, which obviates the need to build a new storehouse for it.
The president of the Washington Group Energy and Environment Division Preston Rahe said that if Washington do succeed in buying BNG it will reopen the THORP (Thermal Oxide Reprocessing Plant) at Sellafield. Now this will strike terror into those many hearts who protested vehemently against THORP being opened in the first place. It was closed last year following the discovery that radioactive material had somehow leaked from it. Washington also intend to continue production of MOX "mixed oxide". MOX is a mixture of Uranium Oxide (U3O8) and Plutonium Oxide (PuO2) fabricated into a fuel for use in nuclear power stations, which is derived from uranium and plutonium extracted from nuclear waste by "reprocessing".
In some respects, THORP is a good thing, since it literally consumes high level nuclear waste, and it can also be used to turn weapons grade uranium (90% uranium 235) and plutonium (239) derived from nuclear warheads into a fuel suitable for peaceful electricity generation. It would be one way to get rid of them all, if humankind wanted this agenda, rather than the U.S., Russia and U.K.'s intention to revamp their respective nuclear arsenals. I have been told that there is enough uranium and plutonium available in warheads in the U.K. to supply us with nuclear generated electricity (using breeder reactors) for 100 years.
Legislation was brought in during the Jimmy Carter period which prevents the export of nuclear waste from the U.S. on the grounds that to do so might encourage nuclear proliferation; however, it is expected that these constraints are likely to be relaxed. This raises the possibility of shipping nuclear waste from the U.S. over here for reprocessing, which Mr Rahe describes as "an interesting and creative idea". I doubt those opposed to THORP in the first place will share his views.
In terms of nuclear proliferation, the nuclear industry in China is rather interesting, and is a good example that the whole picture can't necessarily be viewed from statistics alone. Asia is a growth market for nuclear power, as it is for all other kinds of power required to quench its inexhaustable thirst for industrial growth. From 1996 to 2003, no new reactor was brought on-line in the U.S., nor was any such intention to do so been declared. In contrast, China brought 6 on line, plus another one in Pakistan during that same period. This should nonetheless be viewed in context, and the growth in the use of nuclear power is quite in line with the increased consumption of petroleum (gas has not traditionally featured heavily in China's energy-mix) and coal that has occurred. However, there are more ambitious nuclear plans afoot.
As China wrestles to diversify its energy industry, the consequent ecomonic and political reverberations will be felt around the world; notably in regard to securing an adequate supply of oil as the United States are also thrashing to achieve. Indeed, China's leaders think that using more nuclear power will reduce its reliance on imported foreign oil and help eliminate the palls of smog that burning the former fuel has left hanging over its cities. At present, 9 reactors provide 2% of China's electricity, which is just one eighth of the global average. However, the target is to raise this to 4 percent (40 Gigawatts) over the next 15 years by building 30 new reactors. This means building 2 new reactors every year (I know that's obvious but I thought I would stress the fact), which is quite an ambitious target.
Unlike most other countries, China has an especially mixed range of reactor technologies in operation within its borders, since it has used Canadian, French and Russian designs, and is considering buying another from the U.S. along with developing its own technology. For instance, at Tsinghua University, a "pebble-bed" reactor is being tested, which uses fuel "pebbles" - about the size of tennis balls and wrapped in graphite. It is believed impossible that the nuclear fuel could melt in this arrangement since graphite has a higher melting point than uranium oxide (I'm not sure graphite does actually "melt" in the conventional sense, but vapourises directly?) and acts as a shield over the oxide.
Despite the new research, the usual issues of radioactive waste and nuclear safety (Chernobyl) prevail, and the Chinese government may have trouble persuading utilities to help fund their putative nuclear expansion. To place this in context, a 2 Gigawatt nuclear power plant costs about $3 billion, which needs to be put up front (guaranteed anyway). Disposing of the 1000 tonnes per year of radioactive waste produced by the expanding industry is rather a headache but there are plans to expand a small facility in western Gansu province to deal with much of the spent fuel, although there are fears that in fact it will be the poorest areas that are forced to accommodate the waste in some form or another.
I note that the U.K. government's Chief Scientific Advisor Professor Sir David King is intent that in this country we will have at least one more new generation of nuclear power stations. I have written about this before, but I read it more and more frequently and in various different publications, most lately in "Chemistry World", so it does rather look as though we will maintain our present capacity with new, even if there is no actual proliferation of nuclear power.

Massive New European Wind Farm.

I note this morning that 2,000 wind turbines are to be installed in the southern North Sea by the Irish company Airtricity and ABB, the Swedish based engineering group, which will provide 10 Gigawatts (10,000 Megawatts) of power, sufficient it is thought to supply 8 million homes. This is part of the provision of a European supergrid, linking wind farms from the Baltic Sea, the North Sea, The Irish Sea and the Mediterranean. The great advantage of this system is that essentially the wind will always be blowing somewhere, and it is proposed this will lead to constancy of supply, which is a problem with a conventional wind farm: i.e. either you put up with a very up-and-down supply - which would be no good for most electrical devices such as computers and televisions - or you store the electricity in some way, e.g. by charging batteries of some kind or more nebulously, but as some think, in the form of hydrogen produced from that electricity by the electrolysis of water.
This sounds like a fantastic idea in principle. However, if I understand the proposal correctly, providing 10 Gigawatts (GW) of full capacity wind energy by 2000 turbines means that the capacity of each is: 10 x 10*9/2000 = 5 x 10 *6, or 5 Megawatts (MW). I know that turbines rated at 2 MW exist, but I thought that 5 MW was still on the drawing board, but I guess it will take some time to approve the plan and so the technology might well have moved on by then. O.K.
Now in terms of an actual generating capacity, since turbines don't run at full capacity most of the time, if ever, we need to multiply that figure by the "capacity factor", which is reckoned on considerable Danish and German experience at a maximum of 0.2. In other words we would get 0.2 x 10 GW = 2 GW in total from the 2000 turbine farm. So each home would get 2GW/8 million = 250 watts per unit. Now this is a useful amount, and using energy efficient light bulbs it could certainly light most houses, but it couldn't boil a standard electric kettle (about 2 kW) , but it could boil a lower capacity one if you simply waited about 8 times longer.

The annual electricity consumption of a typical U.K. house is about 3500 kWh/year or about 10 kWh/day. So at 0.25 kW (250 watts), this might supply 0.25 x 24 = 6 kWh/day or 2,200 kWh/year. If we work on more energy efficient devices too, then we are not far off our requirements. I am hopeful that this might work in fact, at least for the purpose of providing a domestic supply.

The 2000 turbines are to be installed in the southern part of the North Sea between Britain, Germany and the Netherlands. The companies involved have emphasised that the construction of the power grid itself will enable free access of electricity trade between European countries, which has always been a hurdle. A cable linking the grids over 1,000 km would stretch the length of an average weather front, and so would collect wind power from each farm contained in the network, to provide a constant level of power for those countries that are linked up to the grid, and get around the "on-off" aspect intrinsic to a single farm, i.e. the peaks and troughs are averaged out to a near constant baseline value.

I think this sounds promising. However, we still need to address the problem of how to substitute for cheap oil, and the cheap fuel that we get from it, in short order. The "super-grid" does not help here, and nor is it intended to. Certainly it would help delay the problem of "Peak Gas" (which much European electricity is made from) the date of which has been revised down to about 2030 from the 2100 I heard originally.

The success of the scheme depends on it getting regulatory support and financial backing from a bank (the European Investment Bank, say) and appropriate industrial partners. I wish it well.

Ponds, Leaks and "Lethal Beams".

According to Nirex, which is responsible for matters related to the storage of Britain's nuclear waste and decommissioning the plants that produced it, a lot more information (and time?) will be necessary before any determined effort can be made to clean-out the "cooling-ponds" at Sellafield, and to decontaminate radioactively polluted land both at Sellafield and other nuclear sites, and to sort-out the leaky waste-shaft at Dounreay, the fast-breeder installation located on the coast of Scotland. Dounreay is the name of a now ruinous castle on the north coast of Caithness, in the Highlands of Scotland, and is 9 miles from Thurso, a town that grew rapidly once the nuclear facility was established.
50 years back, the Sellafield ponds were an integral part of the programme which developed the U.K. into a nuclear power, both in terms of weapons technology and in the 1960's to provide electricity from that first generation of "Magnox" reactors. Now, the NDA (Nuclear Decommissioning Agency) intends to spend a third of its £1 billion budget on emptying them, and remediating any land that has been contaminated by leakage of radioactive material over the long time of their use, a strategy for which will be determined once the extent of this is known.
The "ponds" are radioactive junkyards, which contain machine parts and reactor components such as cladding from the magnox reactors, among others. (I have been told by an "old hand" that there are even old bicycles dumped in them). Two of the ponds are open, and are not a pretty sight. In fairness, the ponds and much of the older construction of the Sellafield facilities belong to a far more cavalier age.
British Nuclear group Sellafield faces a rather more immediate problem, namely a criminal prosecution by The Health and Safety Executive in connection with a serious leak of "radioactive liquor" inside a heavily shielded facility at THORP (the infamous Thermal Oxide Reprocessing Plant). Apparently the material had leaked out for nine months without arousing suspicion, to the extent that there is now enough to fill an olympic-sized smimming pool so radioactive that no-one can go anywhere near it. Since it not feasible to deal with the matter using robots either, I can only guess that it will just have to sit there, hoping that there is no leakage of that plutonium and uranium contaminated "liquor", otherwise the problem will become more urgent.
There is one other - more bizarre - incident too. Apparently an old cancer therapy unit (probably containing cobalt-60, which is an intense gamma-ray emitter) was being carried on the back of a lorry from Leeds to Sellafield for decommissioning. Apparently a safety-cap had inadvertently been left off the cargo before it made its 130 mile journey, sanguinely irradiating the picturesque route as it crossed the Pennines. Luckily, the highly focussed "needle" beam was pointing downwards (as it would for its purpose of irradiating tumours, when you think about the configuration of the procedure) so no harm was done. However, the haulage firm responsible for its transportation was fined £250,000 in February, I guess to make an example of them.
The independent Sellafield watchdog "the West Cumbria Sites Stakeholder Group" is undertaking an enquiry into the incident and its chairman David Moore has reassured the public that nothing of the kind can ever happen again.