So ran the caption to one of René Magritte’s most famous paintings, and at times the debate over the $7 billion Keystone XL pipeline has been as surreal as anything produced by the Belgian master, prompting all manner of ‘Keystone Cops’ (or ‘Keystone Cop-out’) headlines. Originally conceived as a way of carrying up to 830,000 bbl/d of oil sands syncrude from northern Canada to processing facilities on the US Gulf Coast, the 2,700km Keystone XL pipeline was approved in March 2010 but thereafter rapidly became mired in controversy. Local opposition was strongest in Nebraska, where the pipeline was due to pass through the ecologically Sandhills area, but environmental opposition has grown to the entire project. As a trans-national pipeline, a final decision rested with the US State Department, and with an eye to presidential and congressional elections scheduled for November next year, President Obama has decided to kick a decision further down the line, with a State Department review now not scheduled for completion until early 2013. Developer TransCanada had proposed a re-routing of the most contentious section, in Nebraska, but it seems that the re-routing the president desired most was around next year’s election, and fears that the pipeline would become an election issue appear to have made the delay irrevocable.
So what now for Canada’s oil sands? The European Union has recently weighed in with its own contribution to the debate by rating oil sands crude’s global warming potential much higher than conventional crude in its new Fuel Quality Directive, and meanwhile Canada is now seriously considering a pipeline to the coast so that the crude can be exported to energy-hungry China, where environmental concerns loom much lower. But US Gulf refiners have already begun construction of up to 700,000 bbl/d of new capacity to process the syncrude there, so it seems highly likely that some of it will end up there, one way or another.
At this year’s Sulphur Conference in Houston in early November, the whole tangled knot was examined by Chris Smith, Pipelines Editor of Oil and Gas Journal, who looked at the various options for getting the syncrude to the US Gulf. There is still spare capacity in the rail network between the US and Canada, he noted, which could allow between 500,000 and 1.0 million barrels per day to be transported that way. And of course Keystone has all manner of rival pipeline schemes, including the Enbridge Northern Gateway pipeline across British Columbia, allowing oil sands crude to be exported from Kitimat (with China and India major potential customers), and another Enbridge proposal to run from Cushing to Houston, linking up with other pipelines such as ExxonMobil’s Pegasus and Keystone’s Cushing line.
At the moment Canada is looking at an extra 3 million bbl/d of oil sands bitumen production by 2020, containing up to 7.5 million t/a of sulphur, and for the sulphur industry, as described by Jim Hyne in our September/October issue, at stake is whether this 7.5 million t/a of sulphur is extracted in Canada, the southern US, or even in China. At present most syncrude is produced at upgraders in Alberta, and most of the sulphur is extracted during the process, producing a sweet syncrude for export. However, one of the fears of environmental protestors was that the pipeline would carry ‘dilbit’ – a dilute bitumen slurry, with several percent sulphur encapsulated within it. Chris Smith argued that if more rail transport rather than pipeline capacity was used, more bitumen would be transported un-upgraded. His calculations put likely shipments of oil sands crude to the Gulf Coast between 210-700,000 bbl/d, with a figure of 300-400,000 bbl/d most likely, and a mixture of rail and pipeline transport (and hence syncrude and dilbit) being used. Sulphur encapsulated in this mix would be 480,000 – 720,000 t/a, recovered at the Gulf’s refineries.
In spite of environmental objections, Canadian oil sands production currently seems likely to increase no matter what. Whether this results in a sulphur boom for Canada, the US or China – or some combination of all three – has yet to be determined.
Wednesday 7 December 2011
A message to the oil patch - sulphur IS your business
From our guest columnist: 'Thiophilos'
Big Oil’s attitude toward sulphur is not hard to understand. There was a time, not so long ago, that sour natural gas associated with many prolific oil producing fields was routinely flared to atmosphere, until the LNG business become fashionable. The same selectivity as to whether sulphur is an appropriate business to be in has been associated with the more recent heavy oil and oil sands, which have even attracted the moniker of ‘dirty oil’, partly because of their high sulphur content. The simple scientific facts, however, leave little doubt that there is a common factor in all subdivisions of the energy business. In this World Year of Chemistry it is worth noting that the chemical process of “oxidative release of chemically stored energy” is the common factor throughout the spectrum of such “businesses”. If you are involved in one of them then, by association, you are involved in all of them – whether you like it or not.
The earliest days of Oil Patch involvement in the sulphur business came with the desire to rid the sour crudes of their bad smell and even worse effects (corrosion) on production and combustion equipment. The relatively small amounts of sulphur involved were ‘tolerable’ until sweeter crudes began to be harder to find. Half a century ago by far the largest source of elemental sulphur for world industrial needs came from mining of pre-existing elementary sources of the yellow element. It was mined in lock step with the world demand for the stuff, largely for sulphuric acid manufacture.
Then came sour gas and sour oil processing and a huge new source of recovered sulphur. In the middle of the 20th century 70% of the world supply of sulphur was from mined sources (elemental sulphur or mined iron sulphide ore). By the beginning of the 21st century the source situation has reversed: 90%+ of world sulphur supply is recovered from sour hydrocarbon processing. Big Oil is in the sulphur business – Big Time.
If you are at all familiar with the commercial history of either the Oil Patch or the Sulphur Patch over this fifty year period you will also be familiar with the struggles that emerged between the two over the supply and control of the world’s sulphur supply. The US vested interests in the Frasch mining business, the Alberta sour gas recovered sulphur market (producing the element and energy), the rise and fall of the Polish sulphur mining venture and, most recently, the heavy oil and oil sand sulphur sources of both Alberta and Venezuela, again producing both energy and sulphur.
However the sulphur market place may be viewed, the hydrocarbon industry is and will continue to be the prime producer of the element. That is where the ultimate control of supply rests. That is where the challenge to improve recovery efficiency is placed by the environmental protectionists. And that is where the money supply is to be found to establish and maintain the new products and markets that will be essential to maintain a balance between production and consumption of the yellow element in a world wide marketplace.
Sulphur magazine’s market graph tells a tale of instability far more succinctly that any words can hope to do. For the better part of half a century – most of it while the Oil Patch did not have control of the production – the elemental sulphur commodity price fluctuated between $25 - 100/ton f.o.b. production source. Then came the wild times of the past few years; from $100 to $700/ton within months and crashing back down to near zero in an equally short time. Even market economists with the most accommodating of views look at these numbers and gasp in disbelief. “Who was at the controls?” they ask. “How did it happen?” they ponder. And looking at the very recent rise back up to near $250/ton f.o.b., the question is now “Could or even IS it happening again?”
To opine that there has been no answer offered to any of these questions might be unjustified. But to question the explanations that have been offered is nothing if not justified. The considered opinion of Thiophilos is not complex. It is traditional market psychology. The fewer options there are for sales in any market, the less stable that market will be. The vested interests control. And that, dear readers, (and some detractors) is the current situation with respect to the sulphur business. A multimillion ton/annum world wide market with two – yes only two – really significant market outlets, which can be reduced to one of you chose to name it as chemical technology. That single outlet is sulphuric acid, and its two commercial subdivisions are fertilizer/ore processing and as an energy source for the chemical industry. It should be a black eye for the scientific curiosity and inventiveness in this World Year of Chemistry that, with the myriad of sulphur market opportunities staring society in the face, genuinely new uses for the yellow element are as ignored as they are. Many have been identified and written about in the technical media, even advertised as being available commercially. But they remain unattractive to those who claim the lion’s share of profits from the other contents of Mother Nature’s purse from which the really raw materials cometh.
Can we muster the effort, ingenuity and enterprise to break out from our safe established commercial havens in to the exploratory developments that will take us the next step along the road to discovery of new horizons? We may well find that there lie an assembly of riches to match those our forefathers left for us. Look around you at sulphur’s opportunities – many are there.
‘Thiophilos’
Big Oil’s attitude toward sulphur is not hard to understand. There was a time, not so long ago, that sour natural gas associated with many prolific oil producing fields was routinely flared to atmosphere, until the LNG business become fashionable. The same selectivity as to whether sulphur is an appropriate business to be in has been associated with the more recent heavy oil and oil sands, which have even attracted the moniker of ‘dirty oil’, partly because of their high sulphur content. The simple scientific facts, however, leave little doubt that there is a common factor in all subdivisions of the energy business. In this World Year of Chemistry it is worth noting that the chemical process of “oxidative release of chemically stored energy” is the common factor throughout the spectrum of such “businesses”. If you are involved in one of them then, by association, you are involved in all of them – whether you like it or not.
The earliest days of Oil Patch involvement in the sulphur business came with the desire to rid the sour crudes of their bad smell and even worse effects (corrosion) on production and combustion equipment. The relatively small amounts of sulphur involved were ‘tolerable’ until sweeter crudes began to be harder to find. Half a century ago by far the largest source of elemental sulphur for world industrial needs came from mining of pre-existing elementary sources of the yellow element. It was mined in lock step with the world demand for the stuff, largely for sulphuric acid manufacture.
Then came sour gas and sour oil processing and a huge new source of recovered sulphur. In the middle of the 20th century 70% of the world supply of sulphur was from mined sources (elemental sulphur or mined iron sulphide ore). By the beginning of the 21st century the source situation has reversed: 90%+ of world sulphur supply is recovered from sour hydrocarbon processing. Big Oil is in the sulphur business – Big Time.
If you are at all familiar with the commercial history of either the Oil Patch or the Sulphur Patch over this fifty year period you will also be familiar with the struggles that emerged between the two over the supply and control of the world’s sulphur supply. The US vested interests in the Frasch mining business, the Alberta sour gas recovered sulphur market (producing the element and energy), the rise and fall of the Polish sulphur mining venture and, most recently, the heavy oil and oil sand sulphur sources of both Alberta and Venezuela, again producing both energy and sulphur.
However the sulphur market place may be viewed, the hydrocarbon industry is and will continue to be the prime producer of the element. That is where the ultimate control of supply rests. That is where the challenge to improve recovery efficiency is placed by the environmental protectionists. And that is where the money supply is to be found to establish and maintain the new products and markets that will be essential to maintain a balance between production and consumption of the yellow element in a world wide marketplace.
Sulphur magazine’s market graph tells a tale of instability far more succinctly that any words can hope to do. For the better part of half a century – most of it while the Oil Patch did not have control of the production – the elemental sulphur commodity price fluctuated between $25 - 100/ton f.o.b. production source. Then came the wild times of the past few years; from $100 to $700/ton within months and crashing back down to near zero in an equally short time. Even market economists with the most accommodating of views look at these numbers and gasp in disbelief. “Who was at the controls?” they ask. “How did it happen?” they ponder. And looking at the very recent rise back up to near $250/ton f.o.b., the question is now “Could or even IS it happening again?”
To opine that there has been no answer offered to any of these questions might be unjustified. But to question the explanations that have been offered is nothing if not justified. The considered opinion of Thiophilos is not complex. It is traditional market psychology. The fewer options there are for sales in any market, the less stable that market will be. The vested interests control. And that, dear readers, (and some detractors) is the current situation with respect to the sulphur business. A multimillion ton/annum world wide market with two – yes only two – really significant market outlets, which can be reduced to one of you chose to name it as chemical technology. That single outlet is sulphuric acid, and its two commercial subdivisions are fertilizer/ore processing and as an energy source for the chemical industry. It should be a black eye for the scientific curiosity and inventiveness in this World Year of Chemistry that, with the myriad of sulphur market opportunities staring society in the face, genuinely new uses for the yellow element are as ignored as they are. Many have been identified and written about in the technical media, even advertised as being available commercially. But they remain unattractive to those who claim the lion’s share of profits from the other contents of Mother Nature’s purse from which the really raw materials cometh.
Can we muster the effort, ingenuity and enterprise to break out from our safe established commercial havens in to the exploratory developments that will take us the next step along the road to discovery of new horizons? We may well find that there lie an assembly of riches to match those our forefathers left for us. Look around you at sulphur’s opportunities – many are there.
‘Thiophilos’
Wednesday 5 October 2011
Iraq’s rocky road
In early September the Iraq Mining Conference was held in London, showcasing a series of projects for which the Iraqi government is hoping to gain foreign participation and finance. While much development in the country has previously focused on its oil, gas and petrochemical industries, Iraq also has considerable mineral resources, including iron ore, copper, gypsum, dolomite and marble. According to deputy prime minister Dr. Rowsch N. Shaways, the minerals and mining sector contributed just 6% to Iraq’s GDP in 2009 (compared to about 68% for oil, gas and refining), but has the potential to play a far more significant role, reducing dependency on the hydrocarbon sector.
Of particular interest to the sulphur industry are firstly the huge (at least 100 and possibly up to 500 million tonnes) elemental sulphur deposit at al-Mishraq, which prior to the 2003 invasion was producing over a million tonnes of sulphur per year via Frasch mining, and secondly the major phosphate deposits in the west of the country. Of these latter, Greg Fernette, from the US Geological Survey (USGS) told the conference that Iraq possesses “world class” phosphate reserves. The USGS has been working with its Iraqi counterpart Geosurv in a seven year study to map the country’s mineral reserves, and calculates that the two largest phosphate deposits, Akashat and Swab, have 1.7 and 3.5 billion tonnes of ore respectively, at >21% P2O5 content. The four largest deposits, including these two, have 5.75 billion tonnes, or 9% of the world total. The H3 deposit holds 332 million tonnes at an average 17.9% P2O5, and Ethna 218.7 million tonnes at 18.1%. Overall these figures put Iraq’s phosphate deposits at the second largest in the world, after Morocco. Given the current rush towards major phosphate projects in Morocco, Australia and Saudi Arabia, Iraq has the potential to become extremely rich from these reserves.
Prior to the invasion the phosphate mines were producing about 1.0 million tonnes of rock, with downstream phosphoric acid, triple superphosphate and ammonium phosphate capacity which averaged production of 400,000 t/a P2O5. However, the plants at Akashat, in western Iraq are currently only operating at 10% of capacity. According to Dr. Khaldoun al-Bassam, director general of the state-owned Geosurv agency, rehabilitation of the phosphoric acid plant at Akashat is the top priority for the government in the minerals sector. The downstream production site is close to two open-cast phosphate rock mines. At full production, the 1million t/a P2O5 phosphoric acid plant would have a requirement for 6 million t/a phosphate rock and 1.2 million t/a sulphur. The estimated cost of rehabilitating the Akashat facilities is $280 million: in addition to the estimated $130m cost of the phosphoric acid plant, this comprises the beneficiation unit ($30m), the 600,000 t/a TSP plant ($50m), the 280,000 t/a MAP plant ($40m) and the 655,000 t/a NPK facility ($30m). Output from the rehabilitated Akashat complex would be targeted for markets in the Indian sub-continent and elsewhere in Asia.
As for the Mishraq sulphur facility, production also remains at very low levels (possibly zero), and most sales are from remaining above ground stockpiles. The cost of re-commissioning the Mishraq sulphur facility is estimated at $110 million, returning it to a projected capacity of 820,000 t/a of sulphur. No doubt most of this would go to Akashat to feed sulphuric acid production for the phosphate project.
However, as with many things in Iraq, nothing is ever quite so simple. Just as the inking of a hydrocarbons law took long and tortuous years of argument, and the final recent approval of which this August has caused a breach with the northern Kurdish region, so a review of the country’s mining law is still awaited and its lack could prove a stumbling block for new investors. The security situation also remains very difficult in several parts of the country, and there are continuing issues with power and other infrastructure.
The government recognises the difficulty of attracting overseas investment in the current climate, and is offering a 10-year tax holiday for foreign companies, or 15 years if they work in partnership with an Iraqi company. Both the potential rewards, and the risks, are considerable.
Of particular interest to the sulphur industry are firstly the huge (at least 100 and possibly up to 500 million tonnes) elemental sulphur deposit at al-Mishraq, which prior to the 2003 invasion was producing over a million tonnes of sulphur per year via Frasch mining, and secondly the major phosphate deposits in the west of the country. Of these latter, Greg Fernette, from the US Geological Survey (USGS) told the conference that Iraq possesses “world class” phosphate reserves. The USGS has been working with its Iraqi counterpart Geosurv in a seven year study to map the country’s mineral reserves, and calculates that the two largest phosphate deposits, Akashat and Swab, have 1.7 and 3.5 billion tonnes of ore respectively, at >21% P2O5 content. The four largest deposits, including these two, have 5.75 billion tonnes, or 9% of the world total. The H3 deposit holds 332 million tonnes at an average 17.9% P2O5, and Ethna 218.7 million tonnes at 18.1%. Overall these figures put Iraq’s phosphate deposits at the second largest in the world, after Morocco. Given the current rush towards major phosphate projects in Morocco, Australia and Saudi Arabia, Iraq has the potential to become extremely rich from these reserves.
Prior to the invasion the phosphate mines were producing about 1.0 million tonnes of rock, with downstream phosphoric acid, triple superphosphate and ammonium phosphate capacity which averaged production of 400,000 t/a P2O5. However, the plants at Akashat, in western Iraq are currently only operating at 10% of capacity. According to Dr. Khaldoun al-Bassam, director general of the state-owned Geosurv agency, rehabilitation of the phosphoric acid plant at Akashat is the top priority for the government in the minerals sector. The downstream production site is close to two open-cast phosphate rock mines. At full production, the 1million t/a P2O5 phosphoric acid plant would have a requirement for 6 million t/a phosphate rock and 1.2 million t/a sulphur. The estimated cost of rehabilitating the Akashat facilities is $280 million: in addition to the estimated $130m cost of the phosphoric acid plant, this comprises the beneficiation unit ($30m), the 600,000 t/a TSP plant ($50m), the 280,000 t/a MAP plant ($40m) and the 655,000 t/a NPK facility ($30m). Output from the rehabilitated Akashat complex would be targeted for markets in the Indian sub-continent and elsewhere in Asia.
As for the Mishraq sulphur facility, production also remains at very low levels (possibly zero), and most sales are from remaining above ground stockpiles. The cost of re-commissioning the Mishraq sulphur facility is estimated at $110 million, returning it to a projected capacity of 820,000 t/a of sulphur. No doubt most of this would go to Akashat to feed sulphuric acid production for the phosphate project.
However, as with many things in Iraq, nothing is ever quite so simple. Just as the inking of a hydrocarbons law took long and tortuous years of argument, and the final recent approval of which this August has caused a breach with the northern Kurdish region, so a review of the country’s mining law is still awaited and its lack could prove a stumbling block for new investors. The security situation also remains very difficult in several parts of the country, and there are continuing issues with power and other infrastructure.
The government recognises the difficulty of attracting overseas investment in the current climate, and is offering a 10-year tax holiday for foreign companies, or 15 years if they work in partnership with an Iraqi company. Both the potential rewards, and the risks, are considerable.
Tuesday 26 July 2011
Sulphur power
Sulphur is an amazingly versatile element, as this blog never tires of telling people. Fellow poster Thiophilos reminds people of sulphur’s virtues as a power source, utilising the heat of combustion in electricity generation, as happens daily at countless sulphur-burning sulphuric acid plants around the world.
But sulphur is now also set to make other inroads into powering our lives, this time via battery technology. As the number and capability of portable electronic devices continues to increase, our appetite for portable power sources is also growing, and at a staggering rate. Battery technology has already had several step changes over the past few decades, from lead-acid through nickel-cadmium and alkaline cells, to lithium ion batteries, which are the new workhorses of the consumer electronics industry, especially for rechargeable applications like mobile phones, tablets and laptop computers. But the need to increase energy density continues, especially if we are to move to electrically-powered vehicles.
One of the problems is with the cathode of lithium ion batteries, which in the case of lithium oxides or lithium iron phosphate might only have fraction of the specific charge capacity of the silicon or graphite anode. Over the past few years, the focus of attention has turned to sulphur as a cathode – sulphur has a very high theoretical specific capacity. As a result, and also because of the relatively lightweight elements that constitute them, lithium sulphur (Li-S) batteries can have two to four times the energy density of lithium-ion batteries, both in weight and volume terms. However, one of the problems with using sulphur is its poor conductivity, and another is that it tends to form lithium polysulphides which are soluble in the battery electrolyte. This means that the Li-S batteries’ ability to be discharged and recharged rapidly degrades away over several charging cycles.
Commercial Li-S batteries have been under development by several companies, using coated sulphur and electrolytes which minimise the dissolution of the lithium polysulphides, but in the meantime work has been under way in research institutes around the world to completely overcome the issues with Li-S batteries, and now Dr Hailiang Wang and his team at Stanford University in the US say that they may have found a way. The technique that they use is a polyethylene glycol (PEG) coating on sub-micron particles of sulphur. The PEG coating traps polysulphides and prevents them dissolving away. Nanoengineering techniques are then use to wrap the coated particles in a ‘cage’ of graphene molecules. The interaction between the carbon and sulphur renders the particles electrically conducting, and also supports them as they swell and shrink during each charging cycle.
As the paper says: “it is worth noting that the graphene-sulphur composite could be coupled with silicon-based anode materials for rechargeable batteries with significantly higher energy density than currently possible.”
There is clearly a lot of work still to be done before such a technique can be first optimised and then performed on an industrial scale. However, in the meantime the first generation of lithium-sulphur batteries are already being used in demonstration applications. One was used in the world’s longest unmanned flight, using a solar-powered aircraft which stayed aloft for 14 days in July 2010. Companies like Oxis Energy and Sion Power are racing to commercialise Li-S batteries and within a few years it may well be that your mobile phone or tablet computer, and possibly even your car, will be powered by sulphur.
But sulphur is now also set to make other inroads into powering our lives, this time via battery technology. As the number and capability of portable electronic devices continues to increase, our appetite for portable power sources is also growing, and at a staggering rate. Battery technology has already had several step changes over the past few decades, from lead-acid through nickel-cadmium and alkaline cells, to lithium ion batteries, which are the new workhorses of the consumer electronics industry, especially for rechargeable applications like mobile phones, tablets and laptop computers. But the need to increase energy density continues, especially if we are to move to electrically-powered vehicles.
One of the problems is with the cathode of lithium ion batteries, which in the case of lithium oxides or lithium iron phosphate might only have fraction of the specific charge capacity of the silicon or graphite anode. Over the past few years, the focus of attention has turned to sulphur as a cathode – sulphur has a very high theoretical specific capacity. As a result, and also because of the relatively lightweight elements that constitute them, lithium sulphur (Li-S) batteries can have two to four times the energy density of lithium-ion batteries, both in weight and volume terms. However, one of the problems with using sulphur is its poor conductivity, and another is that it tends to form lithium polysulphides which are soluble in the battery electrolyte. This means that the Li-S batteries’ ability to be discharged and recharged rapidly degrades away over several charging cycles.
Commercial Li-S batteries have been under development by several companies, using coated sulphur and electrolytes which minimise the dissolution of the lithium polysulphides, but in the meantime work has been under way in research institutes around the world to completely overcome the issues with Li-S batteries, and now Dr Hailiang Wang and his team at Stanford University in the US say that they may have found a way. The technique that they use is a polyethylene glycol (PEG) coating on sub-micron particles of sulphur. The PEG coating traps polysulphides and prevents them dissolving away. Nanoengineering techniques are then use to wrap the coated particles in a ‘cage’ of graphene molecules. The interaction between the carbon and sulphur renders the particles electrically conducting, and also supports them as they swell and shrink during each charging cycle.
As the paper says: “it is worth noting that the graphene-sulphur composite could be coupled with silicon-based anode materials for rechargeable batteries with significantly higher energy density than currently possible.”
There is clearly a lot of work still to be done before such a technique can be first optimised and then performed on an industrial scale. However, in the meantime the first generation of lithium-sulphur batteries are already being used in demonstration applications. One was used in the world’s longest unmanned flight, using a solar-powered aircraft which stayed aloft for 14 days in July 2010. Companies like Oxis Energy and Sion Power are racing to commercialise Li-S batteries and within a few years it may well be that your mobile phone or tablet computer, and possibly even your car, will be powered by sulphur.
Sulphur as an energy source
[By our guest columnist, 'Thiophilos']
The stimulus for these Last Words has been the ever present suspicion that, since the Oil Patch became the world’s major source of elemental sulphur through socially imposed requirements to get it out of oil, it has become a barely tolerable pain in the butt for its suppliers. Gone are the days when the miners, be they pick and shovel or the Frasch type, produced valued sulphur “because it was needed” not because they had to, or they couldn’t sell their oil - and that is where the money is; the sulphur product is viewed as very much an unfortunate necessity!
What seems to have missed the Oil Patch’s attention is that sulphur, like carbon, is a very important source of energy in its own right. The similarities are striking. We get energy out of sulphur (and its oil patch precursor hydrogen sulphide) by burning it just as we do hydrocarbon and coal (carbon). The product of the combustion is sulphur dioxide instead of carbon dioxide. Both of these combustion products are GHGs (green house gases - as if you didn’t know). Indeed Rachel Carson et al way back fifty years ago were well ahead of Al Gore and company in highlighting the ‘Inconvenient Truth’ of the combustion emissions from the energy recovery processes. Acid Rain came long before Global Warming but the oxidative mechanism that forms the GHGs is rooted in the same human demand – for energy.
So maybe the fact that sulphur has finished up in bed with its oil patch mate as a “dirty” commodity is not all that unusual. But let’s look at just what dirty old sulphur does for us energy-wise:
In its recovery from admixture and/or combination with the hydrocarbon of oil (and gas) it appears as hydrogen sulphide (like hydro-carbon) and is oxidised (burnt) in the Claus Process Reactor. This chemical step differs little from a methane (hydrocarbon) burning furnace and produces large quantities of high quality steam, much of which is used as a process energy source or to generate electrical energy. The parallel with hydrocarbon energy generation is clear. But in sulphur’s case we are just at the beginning of the energy production chain. The end product of sulphur’s combustion is sulphur dioxide, just as carbon/hydrocarbon produces carbon dioxide, the source of global warming. In sulphur’s case, however, we already have a “capture and sequestration” procedure in place. We make sulphuric acid from the sulphur dioxide “waste product” and that acid is one of the most widely used industrial chemicals known to humankind.
If it wasn’t for the millions of tonnes of sulphuric acid available annually for processing ‘phosrock’ ore the fertilizer industry would consume millions of kilowatts of ‘alternative energy’ (electrical) in getting the essential phosphate nutrient out of the rock and into the plant so that the essential human fuel called food would still be plentifully available. Hydrocarbon-based energy sources may have become the essential motivator for automobiles, but sulphur-based energy sources play an equally important role in providing the essential food for humans. The parallels continue!
But, say the critics, the relative amounts of commodities are vastly different. Are they really? Fifty million tonnes per annum of recovered sulphur is an appropriate round figure to use for the world sulphur trade. As recently as two years ago that sulphur touched $800/tonne on world markets. Simple arithmetic using these numbers values the overall sulphur business at forty billion dollars a year. Not a fortune in today’s marketplace, where debts in the trillions are not uncommon, but not to be sneezed at either. At $100/bbl for oil it amounts to the value of four hundred million barrels of oil, or well over a month’s supply of all the hydrocarbon energy imported by the world’s biggest user. That’s a lot of energy from dirty old sulphur.
So the old yellow element is just as deserving of some respect as the black one – coke, coal or the form with hydrogen attached – hydrocarbon. It is a significant energy source as we energy-hungry humans look for ever more of the stuff. And what is even more impressive, we have already found ways to “sequester” the emissions (of sulphur dioxide) and put them to do good additional work in fuelling ‘we the people’ by fertilising the food we eat. Can you think of a comparable end use for carbon dioxide? Soda pop might cause some undesirable burping problems!
‘Thiophilos’
The stimulus for these Last Words has been the ever present suspicion that, since the Oil Patch became the world’s major source of elemental sulphur through socially imposed requirements to get it out of oil, it has become a barely tolerable pain in the butt for its suppliers. Gone are the days when the miners, be they pick and shovel or the Frasch type, produced valued sulphur “because it was needed” not because they had to, or they couldn’t sell their oil - and that is where the money is; the sulphur product is viewed as very much an unfortunate necessity!
What seems to have missed the Oil Patch’s attention is that sulphur, like carbon, is a very important source of energy in its own right. The similarities are striking. We get energy out of sulphur (and its oil patch precursor hydrogen sulphide) by burning it just as we do hydrocarbon and coal (carbon). The product of the combustion is sulphur dioxide instead of carbon dioxide. Both of these combustion products are GHGs (green house gases - as if you didn’t know). Indeed Rachel Carson et al way back fifty years ago were well ahead of Al Gore and company in highlighting the ‘Inconvenient Truth’ of the combustion emissions from the energy recovery processes. Acid Rain came long before Global Warming but the oxidative mechanism that forms the GHGs is rooted in the same human demand – for energy.
So maybe the fact that sulphur has finished up in bed with its oil patch mate as a “dirty” commodity is not all that unusual. But let’s look at just what dirty old sulphur does for us energy-wise:
In its recovery from admixture and/or combination with the hydrocarbon of oil (and gas) it appears as hydrogen sulphide (like hydro-carbon) and is oxidised (burnt) in the Claus Process Reactor. This chemical step differs little from a methane (hydrocarbon) burning furnace and produces large quantities of high quality steam, much of which is used as a process energy source or to generate electrical energy. The parallel with hydrocarbon energy generation is clear. But in sulphur’s case we are just at the beginning of the energy production chain. The end product of sulphur’s combustion is sulphur dioxide, just as carbon/hydrocarbon produces carbon dioxide, the source of global warming. In sulphur’s case, however, we already have a “capture and sequestration” procedure in place. We make sulphuric acid from the sulphur dioxide “waste product” and that acid is one of the most widely used industrial chemicals known to humankind.
If it wasn’t for the millions of tonnes of sulphuric acid available annually for processing ‘phosrock’ ore the fertilizer industry would consume millions of kilowatts of ‘alternative energy’ (electrical) in getting the essential phosphate nutrient out of the rock and into the plant so that the essential human fuel called food would still be plentifully available. Hydrocarbon-based energy sources may have become the essential motivator for automobiles, but sulphur-based energy sources play an equally important role in providing the essential food for humans. The parallels continue!
But, say the critics, the relative amounts of commodities are vastly different. Are they really? Fifty million tonnes per annum of recovered sulphur is an appropriate round figure to use for the world sulphur trade. As recently as two years ago that sulphur touched $800/tonne on world markets. Simple arithmetic using these numbers values the overall sulphur business at forty billion dollars a year. Not a fortune in today’s marketplace, where debts in the trillions are not uncommon, but not to be sneezed at either. At $100/bbl for oil it amounts to the value of four hundred million barrels of oil, or well over a month’s supply of all the hydrocarbon energy imported by the world’s biggest user. That’s a lot of energy from dirty old sulphur.
So the old yellow element is just as deserving of some respect as the black one – coke, coal or the form with hydrogen attached – hydrocarbon. It is a significant energy source as we energy-hungry humans look for ever more of the stuff. And what is even more impressive, we have already found ways to “sequester” the emissions (of sulphur dioxide) and put them to do good additional work in fuelling ‘we the people’ by fertilising the food we eat. Can you think of a comparable end use for carbon dioxide? Soda pop might cause some undesirable burping problems!
‘Thiophilos’
Is the sulphur industry doing its environmental best?
[By our guest columnist, 'Thiophilos']
As we are daily reminded by the media and many others how dirty and polluting the lives we lead have become, it seems only fair that we pause amidst the muck for a moment and examine how much, if anything, we in the sulphur business have done to clean up the mess in, say, the last couple of generations. Not withstanding the black picture painted by the Greens, it turns out that, by and large, we have not been altogether asleep at the switch. It is more a matter that the faster the industry has become cleaner, the more the people who produce the emissions have grown larger in numbers. The result - more emissions.
In the specific case of elemental sulphur, the world’s annual production of the yellow stuff has blossomed from around 3 million t/a in 1940 to well over 50 million t/a in 2010. To be fair, that growth in sulphur is offset by a reduction in the amount of iron sulphide (pyrites) that is roasted to form sulphur dioxide; that source has been displaced by burning elemental sulphur to produce the same gas to feed sulphuric acid plants. But it is still a huge increase, and one that was enough to get Rachel Carson all upset in the 1960s about the negative effect that all of that fugitive sulphur dioxide was having on Mother Nature.
A good swift rap on the knuckles or boot in the pants never did much harm, and Rachel’s cry for decency on behalf of the industry had a salutary effect. Sulphur recovery plant efficiency rose from a 70-80% level in the 1960-1970 era to near 99% in the early years of the twenty-first century. Not a bad record, but still not enough to satisfy the bright Greens.
To make the challenge to the industry to clean up their act a bit more ‘persuasive’, the folks that design and manufacture analytical testing equipment have moved ahead, by a few orders of magnitude. The sensitivity they can achieve when it comes to detecting the “stuff that got away” has skyrocketed. PPM limits have now become PPB and, at least in the nuclear world, PPTs are now the fashion and eminently measureable. What levels of what emissions are hazardous to your health? It is becoming close to a case of: “if we can measure it, it must be harmful”.
And then there are the bureaucrats who keep adding new regulations to old rules that were based on common sense. Recently the International Maritime Organization (IMO) told us that the cargoes of formed sulphur that we load by the millions of tons for ocean transportation must be “non-combustible”, or nearly so. This notwithstanding the fact that the first thing the buyer does with 95% of the stuff on receipt is to BURN it! Other regulatory bodies see fit to argue that storing formed elemental sulphur in open air stockpiles exposed to wind and rain is no less environmentally friendly than storing it under cover and protected from the other kind of ‘elements’. Who and what is a poor sulphur marketer to believe? The best of intentions may be the very stuff that public criticism is made of.
But there is one thing that sulphur peddlers can be assured of: if you stop trying to be good neighbours the criticism will only get louder. And there is much yet to be done by way of improving sulphur’s image in the eyes of society. Sulphur is a bit like the sun - everybody enjoys its benefits, but they can be brutally antagonistic when exposure to too much of it hurts. It all depends on how the sulphur or solar message is spun by the messenger with the story to tell. Winter holidays under a sun-filled sky are very much OK, but the fact that you are sitting under an unshielded monstrous nuclear reactor that is pouring out harmful radiation is seldom heard. With sulphur the soil acidifying evils and air polluting sulphur dioxide gas emissions are well publicised, but relatively little is heard of the critical role it plays in producing the fertilizer that grows the food which billions eat each and every year of their lives.
And there is even more opportunity for sulphur in the “better life” of the future if we the people would only take time to be more conscious of the chemistry that lies hidden within this common element. Mother Nature has made it a very central component of her photosynthesis systems where she captures all these nuclear sourced rays from the sun and uses the energy to build new living substances. The muscles in your body would not work very well if there were no sulphur-sulphur bonds to make and break in biochemical processes.
It all seems too heavy stuff for the ordinary bloke to be concerned about, but somebody will latch on to some aspect of the story that can be spun into a negative image. Maybe in this official World Year Of Chemistry, we in the sulphur business can do a little teaching of the truth about thios as part of our effort to persuade society that the industry is doing its best to protect the environment, not withstanding the tales of terror told by the television.
‘Thiophilos’
As we are daily reminded by the media and many others how dirty and polluting the lives we lead have become, it seems only fair that we pause amidst the muck for a moment and examine how much, if anything, we in the sulphur business have done to clean up the mess in, say, the last couple of generations. Not withstanding the black picture painted by the Greens, it turns out that, by and large, we have not been altogether asleep at the switch. It is more a matter that the faster the industry has become cleaner, the more the people who produce the emissions have grown larger in numbers. The result - more emissions.
In the specific case of elemental sulphur, the world’s annual production of the yellow stuff has blossomed from around 3 million t/a in 1940 to well over 50 million t/a in 2010. To be fair, that growth in sulphur is offset by a reduction in the amount of iron sulphide (pyrites) that is roasted to form sulphur dioxide; that source has been displaced by burning elemental sulphur to produce the same gas to feed sulphuric acid plants. But it is still a huge increase, and one that was enough to get Rachel Carson all upset in the 1960s about the negative effect that all of that fugitive sulphur dioxide was having on Mother Nature.
A good swift rap on the knuckles or boot in the pants never did much harm, and Rachel’s cry for decency on behalf of the industry had a salutary effect. Sulphur recovery plant efficiency rose from a 70-80% level in the 1960-1970 era to near 99% in the early years of the twenty-first century. Not a bad record, but still not enough to satisfy the bright Greens.
To make the challenge to the industry to clean up their act a bit more ‘persuasive’, the folks that design and manufacture analytical testing equipment have moved ahead, by a few orders of magnitude. The sensitivity they can achieve when it comes to detecting the “stuff that got away” has skyrocketed. PPM limits have now become PPB and, at least in the nuclear world, PPTs are now the fashion and eminently measureable. What levels of what emissions are hazardous to your health? It is becoming close to a case of: “if we can measure it, it must be harmful”.
And then there are the bureaucrats who keep adding new regulations to old rules that were based on common sense. Recently the International Maritime Organization (IMO) told us that the cargoes of formed sulphur that we load by the millions of tons for ocean transportation must be “non-combustible”, or nearly so. This notwithstanding the fact that the first thing the buyer does with 95% of the stuff on receipt is to BURN it! Other regulatory bodies see fit to argue that storing formed elemental sulphur in open air stockpiles exposed to wind and rain is no less environmentally friendly than storing it under cover and protected from the other kind of ‘elements’. Who and what is a poor sulphur marketer to believe? The best of intentions may be the very stuff that public criticism is made of.
But there is one thing that sulphur peddlers can be assured of: if you stop trying to be good neighbours the criticism will only get louder. And there is much yet to be done by way of improving sulphur’s image in the eyes of society. Sulphur is a bit like the sun - everybody enjoys its benefits, but they can be brutally antagonistic when exposure to too much of it hurts. It all depends on how the sulphur or solar message is spun by the messenger with the story to tell. Winter holidays under a sun-filled sky are very much OK, but the fact that you are sitting under an unshielded monstrous nuclear reactor that is pouring out harmful radiation is seldom heard. With sulphur the soil acidifying evils and air polluting sulphur dioxide gas emissions are well publicised, but relatively little is heard of the critical role it plays in producing the fertilizer that grows the food which billions eat each and every year of their lives.
And there is even more opportunity for sulphur in the “better life” of the future if we the people would only take time to be more conscious of the chemistry that lies hidden within this common element. Mother Nature has made it a very central component of her photosynthesis systems where she captures all these nuclear sourced rays from the sun and uses the energy to build new living substances. The muscles in your body would not work very well if there were no sulphur-sulphur bonds to make and break in biochemical processes.
It all seems too heavy stuff for the ordinary bloke to be concerned about, but somebody will latch on to some aspect of the story that can be spun into a negative image. Maybe in this official World Year Of Chemistry, we in the sulphur business can do a little teaching of the truth about thios as part of our effort to persuade society that the industry is doing its best to protect the environment, not withstanding the tales of terror told by the television.
‘Thiophilos’
So much for Peak Phosphorus?
Spring is always a season of conferences, and I seem to have been on my travels more than usual over the past few months, to San Antonio for the National Petroleum Refiners Association’s (NPRA) annual get-together, to Abu Dhabi for the Sour Oil and Gas Advanced Technology (SOGAT) conference, and to New York, where The Sulphur Institute (TSI) had its annual meeting. While picking out the highlights in terms of implications for the industry and the wider world, to my own mind one of the most significant things that I learned over the past two months is that we don’t need to worry about running out of phosphorus.
This is no idle concern; while for the sulphur industry phosphate fertilizers represent 55% of all sulphur and sulphuric acid demand, for the human race it is one of the key nutrients that goes to make up our own bodies – the most common mineral element in us apart from calcium. The Peak Phosphorus debate – like concerns about a number of strategic minerals – has come hard on the heels of Peak Oil fears, but the implications were always perhaps even more worrying; while it might be difficult and expensive, we can always find substitute fuels for oil, or other ways of getting about, but there is no substitute for the role that phosphorus plays in human health and nutrition.
So the prospect of running out of this vital nutrient should perhaps have raised far more global concern than it has done. Warnings began to emerge in 2006 that we would see peak phosphorus production before 2030, with the planet completely denuded of vital phosphate resources by 2050-2100, with the prospect of mass starvation ahead for humanity, and the price peak of 2008 helped give legs to the story. Well, if it did all pass you by, let me tell you that you can relax; it turns out we’re not running out of phosphorus after all. Steven Von Kauwenbergh, phosphate geologist and principal scientist with the International Fertilizer Development Centre, has spent the past couple of years reviewing the evidence for global phosphorus reserves, and at the TSI conference in New York he told me that concerns have been overblown. In fact even economically recoverable reserves – which he puts at 60 billion tonnes – should last us at least 375 years at current rates of usage, and he estimates that global phosphate resources probably total 290 billion tonnes; enough to last 1,800 years at present rates of use. And this is, he insists, a conservative estimate; Morocco alone may have 56 billion tonnes of mineable reserves and 140 billion tonnes of total resources.
The Hubbert Curve is of course a simple mathematical model, with no scope for new technological developments which can have dramatic consequences (such as the way shale gas has transformed the natural gas market). But it is also part of the more general problem of assuming that the future is amenable to a simple extrapolation from present trends. The idea that consumption will always continue to rise is one such. For example, per capita consumption of phosphorus is not rising, but in fact falling. In 1976 it was predicted that we would be using 210 million t/a of phosphates by 2000. The figure for 2000 was actually about 160 million, and like most fertilizer nutrients, consumption has been falling in the developed world since about 1990 as we find more efficient ways of using it. Peak usage in the developing world may not be too far down the line.
Dire predictions about the future, always advanced with the best of intentions, are nothing new. And they often draw our attention to a situation which if left unchecked could indeed be problematic, or contain within them sensible ideas that we should pay heed to. It would be very much to our advantage to continue to try to improve the efficiency of our use of phosphorus, for example. However, it is reassuring to know that this doomsday scenario in particular is not one we need lose much sleep over.
This is no idle concern; while for the sulphur industry phosphate fertilizers represent 55% of all sulphur and sulphuric acid demand, for the human race it is one of the key nutrients that goes to make up our own bodies – the most common mineral element in us apart from calcium. The Peak Phosphorus debate – like concerns about a number of strategic minerals – has come hard on the heels of Peak Oil fears, but the implications were always perhaps even more worrying; while it might be difficult and expensive, we can always find substitute fuels for oil, or other ways of getting about, but there is no substitute for the role that phosphorus plays in human health and nutrition.
So the prospect of running out of this vital nutrient should perhaps have raised far more global concern than it has done. Warnings began to emerge in 2006 that we would see peak phosphorus production before 2030, with the planet completely denuded of vital phosphate resources by 2050-2100, with the prospect of mass starvation ahead for humanity, and the price peak of 2008 helped give legs to the story. Well, if it did all pass you by, let me tell you that you can relax; it turns out we’re not running out of phosphorus after all. Steven Von Kauwenbergh, phosphate geologist and principal scientist with the International Fertilizer Development Centre, has spent the past couple of years reviewing the evidence for global phosphorus reserves, and at the TSI conference in New York he told me that concerns have been overblown. In fact even economically recoverable reserves – which he puts at 60 billion tonnes – should last us at least 375 years at current rates of usage, and he estimates that global phosphate resources probably total 290 billion tonnes; enough to last 1,800 years at present rates of use. And this is, he insists, a conservative estimate; Morocco alone may have 56 billion tonnes of mineable reserves and 140 billion tonnes of total resources.
The Hubbert Curve is of course a simple mathematical model, with no scope for new technological developments which can have dramatic consequences (such as the way shale gas has transformed the natural gas market). But it is also part of the more general problem of assuming that the future is amenable to a simple extrapolation from present trends. The idea that consumption will always continue to rise is one such. For example, per capita consumption of phosphorus is not rising, but in fact falling. In 1976 it was predicted that we would be using 210 million t/a of phosphates by 2000. The figure for 2000 was actually about 160 million, and like most fertilizer nutrients, consumption has been falling in the developed world since about 1990 as we find more efficient ways of using it. Peak usage in the developing world may not be too far down the line.
Dire predictions about the future, always advanced with the best of intentions, are nothing new. And they often draw our attention to a situation which if left unchecked could indeed be problematic, or contain within them sensible ideas that we should pay heed to. It would be very much to our advantage to continue to try to improve the efficiency of our use of phosphorus, for example. However, it is reassuring to know that this doomsday scenario in particular is not one we need lose much sleep over.
Tuesday 5 April 2011
Formed solid sulphur - the market criticality of quality
[By our guest columnist, 'Thiophilos']
Far from being a new topic of conversation, the quality of the various types of formed solid elemental sulphur available on today’s world markets nonetheless remains an important one for a variety of reasons. We live with a market that varies from boom to bust in a short few months, as was seen a couple of years ago. Predictions are for massive oversupply as energy producers drill into higher sulphur content sources of hydrocarbons. Surely competitive advantages such as product quality remain important factors in determining whether your product sells or doesn’t – and how much it sells for?
It used to be that when the market talked quality with respect to bulk solid sulphur it was chemical purity that was in mind; what was the ‘ash’ content? - meaning all the contaminant minerals present that shouldn’t be, or what was the ‘carbon’ content? - focusing on how much hydrocarbon had found its way into the not so bright yellow sulphur for sale. Or trace quantities of arsenic, selenium and tellurium (AST) that weren’t popular with the fertilizer manufacturers that converted it into sulphuric acid for phosphate production. And even the moisture content - great for keeping dust emissions down during handling and transportation but bad news for wet sulphur corrosion of iron-containing vessels that stored or transported the stuff, like marine bulk carriers. And there are more quality offending chemicals on the impurity list.
These impurities are still on the buyers ‘no-no’ list, or at least are reasons for substantial discounts to whatever the market price may be at the time. But with 50 million plus tons of the stuff moving annually through world transportation systems, another important quality feature has emerged in the solid formed version of the yellow element - its physical handling and storage characteristics. How does it respond to rough handling in bulk? Does it crush easily? Do such properties change with time in storage – the ageing process? Is it a big generator of fugitive dust emissions? Are these emissions hazardous with respect to fires, explosions or environmental impact? It is a whole new ball game as far as what is meant by quality of product.
Is this more recent emergence of a different set of quality factors for bulk formed solid elemental sulphur a valid development? It is hardly a new development. For many decades in the twentieth century it was one of the strong arguments in favour of storing and moving elemental sulphur in its liquid form. But this was in the days when sulphur was mined (Frasch) to meet market demand, not as an involuntary by-product of hydrocarbon oil refining. The buyers in those days were also well equipped to receive and handle the hot liquid product, more so than many of today’s developing countries, who import the stuff to make the acid to produce the fertilizer to feed the billions. All this on top of the specialised nature of the heated tankers needed to haul the molten sulphur half way around the world.
So what are the driving forces behind the inclusion of physical handling and storage characteristics in the Quality Factor? From a public relations and social responsibility standpoint it must surely be environmental impact. There is little doubt that if the handling of formed solid elemental sulphur generates significant quantities of fugitive dust particulates, it is hazardous on at least two counts; first the potential for fires and explosions, with all the implied safety and insurance consequences; and second, the ease of aerobic oxidation of the dust to form acid (rain) with all of its negative effects on green and growing matter – animal and vegetable and even mineral.
So what have we been doing about responding to this quality challenge for formed solid elemental sulphur? Quite a lot. A generation ago a whole bunch of world trade solid sulphur was still being moved and stored in what was called “crushed bulk” form. Many of today’s dealers in bulk sulphur are probably too young to recall the fugitive emissions from a windblown pile of crushed bulk sulphur being pushed by a bulldozer or conveyor loaded to railcar or marine bulk carrier, but it was an activity with lots of environmental impact! The era of development of higher quality formed solid sulphur began first with slate or flake, then the various wet forms that led to the granules, pastilles and prills that came to be labelled as the Premium Product that we see more and more on today’s world markets.
But just as the quality of the formed solid sulphur product has risen on the environmental and safety scales, so also have the demands of the global jurisdictions into which the bulk solid sulphur is sold. Fine particulate emissions of sulphur oxidise to acid more quickly, corrode metals more aggressively, threaten lung damage for those who breathe it and tend to burn or explode with a bigger bang. None of the above are deemed acceptable in 21st century commodity businesses. The closer we approach the 100% containment goal, the more the best and most willing buyers demand even better efforts to be really safe and environmentally friendly.
So the message is clear: the solid sulphur industry deserves credit for its work to date but, in this era of ever-increasing competition for a place in the market , the buyers are exercising their long established right to demand the best Quality for the least cost, and achieving that goal is an ever-present challenge for the solid sulphur forming industry.
‘Thiophilos’
Far from being a new topic of conversation, the quality of the various types of formed solid elemental sulphur available on today’s world markets nonetheless remains an important one for a variety of reasons. We live with a market that varies from boom to bust in a short few months, as was seen a couple of years ago. Predictions are for massive oversupply as energy producers drill into higher sulphur content sources of hydrocarbons. Surely competitive advantages such as product quality remain important factors in determining whether your product sells or doesn’t – and how much it sells for?
It used to be that when the market talked quality with respect to bulk solid sulphur it was chemical purity that was in mind; what was the ‘ash’ content? - meaning all the contaminant minerals present that shouldn’t be, or what was the ‘carbon’ content? - focusing on how much hydrocarbon had found its way into the not so bright yellow sulphur for sale. Or trace quantities of arsenic, selenium and tellurium (AST) that weren’t popular with the fertilizer manufacturers that converted it into sulphuric acid for phosphate production. And even the moisture content - great for keeping dust emissions down during handling and transportation but bad news for wet sulphur corrosion of iron-containing vessels that stored or transported the stuff, like marine bulk carriers. And there are more quality offending chemicals on the impurity list.
These impurities are still on the buyers ‘no-no’ list, or at least are reasons for substantial discounts to whatever the market price may be at the time. But with 50 million plus tons of the stuff moving annually through world transportation systems, another important quality feature has emerged in the solid formed version of the yellow element - its physical handling and storage characteristics. How does it respond to rough handling in bulk? Does it crush easily? Do such properties change with time in storage – the ageing process? Is it a big generator of fugitive dust emissions? Are these emissions hazardous with respect to fires, explosions or environmental impact? It is a whole new ball game as far as what is meant by quality of product.
Is this more recent emergence of a different set of quality factors for bulk formed solid elemental sulphur a valid development? It is hardly a new development. For many decades in the twentieth century it was one of the strong arguments in favour of storing and moving elemental sulphur in its liquid form. But this was in the days when sulphur was mined (Frasch) to meet market demand, not as an involuntary by-product of hydrocarbon oil refining. The buyers in those days were also well equipped to receive and handle the hot liquid product, more so than many of today’s developing countries, who import the stuff to make the acid to produce the fertilizer to feed the billions. All this on top of the specialised nature of the heated tankers needed to haul the molten sulphur half way around the world.
So what are the driving forces behind the inclusion of physical handling and storage characteristics in the Quality Factor? From a public relations and social responsibility standpoint it must surely be environmental impact. There is little doubt that if the handling of formed solid elemental sulphur generates significant quantities of fugitive dust particulates, it is hazardous on at least two counts; first the potential for fires and explosions, with all the implied safety and insurance consequences; and second, the ease of aerobic oxidation of the dust to form acid (rain) with all of its negative effects on green and growing matter – animal and vegetable and even mineral.
So what have we been doing about responding to this quality challenge for formed solid elemental sulphur? Quite a lot. A generation ago a whole bunch of world trade solid sulphur was still being moved and stored in what was called “crushed bulk” form. Many of today’s dealers in bulk sulphur are probably too young to recall the fugitive emissions from a windblown pile of crushed bulk sulphur being pushed by a bulldozer or conveyor loaded to railcar or marine bulk carrier, but it was an activity with lots of environmental impact! The era of development of higher quality formed solid sulphur began first with slate or flake, then the various wet forms that led to the granules, pastilles and prills that came to be labelled as the Premium Product that we see more and more on today’s world markets.
But just as the quality of the formed solid sulphur product has risen on the environmental and safety scales, so also have the demands of the global jurisdictions into which the bulk solid sulphur is sold. Fine particulate emissions of sulphur oxidise to acid more quickly, corrode metals more aggressively, threaten lung damage for those who breathe it and tend to burn or explode with a bigger bang. None of the above are deemed acceptable in 21st century commodity businesses. The closer we approach the 100% containment goal, the more the best and most willing buyers demand even better efforts to be really safe and environmentally friendly.
So the message is clear: the solid sulphur industry deserves credit for its work to date but, in this era of ever-increasing competition for a place in the market , the buyers are exercising their long established right to demand the best Quality for the least cost, and achieving that goal is an ever-present challenge for the solid sulphur forming industry.
‘Thiophilos’
Long hot summer?
The convulsions that have gripped the Middle East and North Africa in recent months are another salutary reminder of the meaning of the phrase ‘political risk’. The removal of president Ben Ali in Tunisia appears to have been fortunately - relatively - bloodless, and in Egypt after an initial heavy-handed crackdown by state police the army appears to have stepped into ensure an orderly transition of power from president Hosni Mubarak. Libya, however, with a ruler far less amenable to outside or indeed domestic pressure, has descended into a de facto civil war, while at time of writing, Bahrain has declared a three-month state of emergency and invited Saudi and other troops from its Gulf Cooperation Council partners onto the streets. Yemen is on the brink, and in Morocco, Oman, Jordan, Kuwait, Iran and Saudi Arabia itself, there have been demonstrations and riots, and things remain tense. The Arabic-speaking world appears to be in for a long, hot summer of discontent as high food prices, unemployment, inequalities of wealth, long-standing political grievances and modern communications technology all combine to create a dangerous cocktail.
As fighting rages around the oil terminals at Brega and Ras Lanuf in Libya, and oil prices climb 25% to $120/barrel, minds are bound to be concentrated on the prospects for production disruptions across the region. Some 60% of the world’s oil and 45% of natural gas resources lie within the region, and the prospect of a revolution spreading to Saudi Arabia must keep many people awake at night. Libya is only the world’s 12th largest oil producer, yet markets are clearly nervous. Even if another major oil producer is not sucked into the swirl of political unrest, the ability of the region to generate an oil shock for the global economy in 2011 comparable with that of 2008 is clearly already present, in a world already in an uncertain emergence from recession.
Fertilizer and sulphur markets have been relatively free from disruption so far, but five of the top ten sulphur exporters and three of the largest consumers lie within the region, the former in the oil and gas-rich Gulf region, and the latter based around the major concentrations of phosphate reserves, in the Maghreb and Jordan. Supplies of phosphate rock and downstream fertilizers from GCT, Tunisia were disrupted for some time after the change in government, as labour disputes at the Sfax, Gabes and La Skhira production sites continued. It was reported that production at the GCT 330,000 t/a DAP plant was continuing at just one-third of normal capacity. There are signs that output is resuming but several weeks’ production has been lost.
In ‘Anna Karenina’, Tolstoy said that; “all happy families are alike, but every unhappy family is unhappy in its own way”. This seems to be equally true for unhappy nations; the very different experiences of neighbouring Tunisia and Libya are testament enough to that. The events of one country are not necessarily a guide to what will happen in another, as circumstances can be very different even in the closest neighbours. Some countries in the region, for example, have the cushion of oil reserves – in Saudi Arabia King Abdullah has already spent $36 billion of his windfall gains from high oil prices on buying off dissent. But while the bloodshed of the Libyan civil war appears to have given a temporary pause to some of the momentum for change elsewhere, that momentum nevertheless remains. To concentrate solely on the balance sheet is to eclipse the wider significance of a protest movement which many have compared to those that swept Europe and North America in 1968, or central and eastern Europe in 1989. Regional dictators like Mubarak have often held up the spectre of radical Islamism to justify their position to a West that has often been only too happy to indulge them, but there is clearly a secular rather than sectarian mood afoot. Where the pieces of the puzzle will fall remains an open question, but may well end up reshaping an entire region.
As fighting rages around the oil terminals at Brega and Ras Lanuf in Libya, and oil prices climb 25% to $120/barrel, minds are bound to be concentrated on the prospects for production disruptions across the region. Some 60% of the world’s oil and 45% of natural gas resources lie within the region, and the prospect of a revolution spreading to Saudi Arabia must keep many people awake at night. Libya is only the world’s 12th largest oil producer, yet markets are clearly nervous. Even if another major oil producer is not sucked into the swirl of political unrest, the ability of the region to generate an oil shock for the global economy in 2011 comparable with that of 2008 is clearly already present, in a world already in an uncertain emergence from recession.
Fertilizer and sulphur markets have been relatively free from disruption so far, but five of the top ten sulphur exporters and three of the largest consumers lie within the region, the former in the oil and gas-rich Gulf region, and the latter based around the major concentrations of phosphate reserves, in the Maghreb and Jordan. Supplies of phosphate rock and downstream fertilizers from GCT, Tunisia were disrupted for some time after the change in government, as labour disputes at the Sfax, Gabes and La Skhira production sites continued. It was reported that production at the GCT 330,000 t/a DAP plant was continuing at just one-third of normal capacity. There are signs that output is resuming but several weeks’ production has been lost.
In ‘Anna Karenina’, Tolstoy said that; “all happy families are alike, but every unhappy family is unhappy in its own way”. This seems to be equally true for unhappy nations; the very different experiences of neighbouring Tunisia and Libya are testament enough to that. The events of one country are not necessarily a guide to what will happen in another, as circumstances can be very different even in the closest neighbours. Some countries in the region, for example, have the cushion of oil reserves – in Saudi Arabia King Abdullah has already spent $36 billion of his windfall gains from high oil prices on buying off dissent. But while the bloodshed of the Libyan civil war appears to have given a temporary pause to some of the momentum for change elsewhere, that momentum nevertheless remains. To concentrate solely on the balance sheet is to eclipse the wider significance of a protest movement which many have compared to those that swept Europe and North America in 1968, or central and eastern Europe in 1989. Regional dictators like Mubarak have often held up the spectre of radical Islamism to justify their position to a West that has often been only too happy to indulge them, but there is clearly a secular rather than sectarian mood afoot. Where the pieces of the puzzle will fall remains an open question, but may well end up reshaping an entire region.
Tuesday 1 February 2011
The temperature of sulphur
[By our guest columnist, 'Thiophilos']
If any one person in the sulphur business was on top of the matter of measuring and interpreting the temperature of sulphur it was surely Earnie Emery, whose initials became his company name E2T, synonymous with Claus front end reaction furnace measurement in sulphur recovery systems. Earnie passed on late last year and it seems timely that this Sulphur column take the opportunity to both recognise Earnie’s contributions and the critical importance of measuring, understanding and controlling temperatures throughout the sulphur recovery process.
The Claus reaction furnace has been called the ‘heart’ of the SRU, in the thousands of such units that collect sulphur from where Mother Nature put a lot of it, to make it available to mankind where it is needed in this day and age of major commodity economics. The values of “T” in such units are well into the 1,000C plus range; hardly a trivial challenge to measure with confidence and accuracy. To make matters even more challenging, the chemical reactions that generate these temperatures produce conditions that are, to say the least of it, hard on the construction and measurement materials. But Earnie, with his background in rocket propulsion technology, was up to the task with his focus on infra-red radiation probes and their quantifiable sensitivity to the temperature of the generating source. So much of the early approach to Claus front end furnace technology regarded the unit as a waste disposal technology rather than a sophisticated and relatively complex chemical reactor whose efficiency depended very much on the monitoring and control of its operating temperature.
Earnie and others asked: at what temperature did you optimize the combustion product sulphur dioxide/ hydrogen sulphide ratio to feed to the downstream catalytic conversion units? At what temperature did the firebox lining, burner tips and tube sheet walls start to show unacceptable wear and tear? How much hydrogen was being produced in the furnace by direct thermal cracking of hydrogen sulphide for later use as a reducing agent to reduce emissions? How did ammonia and COS production vary with temperature? How valuable would so called “waste heat” from the FEF high temperature operation in the overall thermodynamics of an optimally functioning furnace be?
All of these (and more) factors became very much more relevant as the struggle to improve overall Claus efficiency from a barely adequate 70% sulphur recovery to the 99% target in today’s systems that is required to meet environmental standards. So often we forget that these kinds of targets can only be achieved if pioneers such as Earnie Emery have had the smarts to apply technology that helped lead from the rocket propelled way to the moon landing to the more mundane but, in its own, way equally important eco-friendly production of the stuff that makes the stuff that grows the stuff we eat?
Earnie’s efforts focused on the FEF and its temperature measurement and control, but it also drew attention to the more general importance of the temperature parameter in many other components of the sulphur production system. The efficiency of the catalytic stages of the Claus redox system which react the hydrogen sulphide and sulphur dioxide from the front end furnace to produce elemental sulphur are critically temperature dependent. Earnie’s infra red thermometers might not have such a seminal role inside a catalyst bed, but they sure worked in keeping an IR eye on the external temperature gradients on the outside of the reactor bed. Catalyst activity drops off inside the charge and the heat of reaction drops and this can be detected on the outside shell. We have a problem inside; let’s fix it and keep the recovery up in the high nineties. Stands to reason. Oh that more of us humans had a better handle on this essential of all civilised activities – reasoning.
But there is still more about the role of temperature in the overall sulphur business. There are few if any other chemical elements that go through as many fundamental changes as sulphur in such a readily accessible temperature range. Its orthorhombic solid crystalline form ‘morphs’ to monoclinic before melting to liquid cyclooctasulphur at 119C. As it heats up to 159C its eight-membered ring molecules break up and reform into a variety of so called Sx species, and finally into long chain polymers which hugely affect its viscosity and fluidity. When it cools down again to solidify, all these species have to reverse themselves and do so at a variety of rates leading to very complex solid sulphur mixtures which can effect the handling and storage properties! Who said temperature control wasn’t a critical factor in the sulphur business?
Thank you, Earnie Emery for your contribution.
‘Thiophilos’
If any one person in the sulphur business was on top of the matter of measuring and interpreting the temperature of sulphur it was surely Earnie Emery, whose initials became his company name E2T, synonymous with Claus front end reaction furnace measurement in sulphur recovery systems. Earnie passed on late last year and it seems timely that this Sulphur column take the opportunity to both recognise Earnie’s contributions and the critical importance of measuring, understanding and controlling temperatures throughout the sulphur recovery process.
The Claus reaction furnace has been called the ‘heart’ of the SRU, in the thousands of such units that collect sulphur from where Mother Nature put a lot of it, to make it available to mankind where it is needed in this day and age of major commodity economics. The values of “T” in such units are well into the 1,000C plus range; hardly a trivial challenge to measure with confidence and accuracy. To make matters even more challenging, the chemical reactions that generate these temperatures produce conditions that are, to say the least of it, hard on the construction and measurement materials. But Earnie, with his background in rocket propulsion technology, was up to the task with his focus on infra-red radiation probes and their quantifiable sensitivity to the temperature of the generating source. So much of the early approach to Claus front end furnace technology regarded the unit as a waste disposal technology rather than a sophisticated and relatively complex chemical reactor whose efficiency depended very much on the monitoring and control of its operating temperature.
Earnie and others asked: at what temperature did you optimize the combustion product sulphur dioxide/ hydrogen sulphide ratio to feed to the downstream catalytic conversion units? At what temperature did the firebox lining, burner tips and tube sheet walls start to show unacceptable wear and tear? How much hydrogen was being produced in the furnace by direct thermal cracking of hydrogen sulphide for later use as a reducing agent to reduce emissions? How did ammonia and COS production vary with temperature? How valuable would so called “waste heat” from the FEF high temperature operation in the overall thermodynamics of an optimally functioning furnace be?
All of these (and more) factors became very much more relevant as the struggle to improve overall Claus efficiency from a barely adequate 70% sulphur recovery to the 99% target in today’s systems that is required to meet environmental standards. So often we forget that these kinds of targets can only be achieved if pioneers such as Earnie Emery have had the smarts to apply technology that helped lead from the rocket propelled way to the moon landing to the more mundane but, in its own, way equally important eco-friendly production of the stuff that makes the stuff that grows the stuff we eat?
Earnie’s efforts focused on the FEF and its temperature measurement and control, but it also drew attention to the more general importance of the temperature parameter in many other components of the sulphur production system. The efficiency of the catalytic stages of the Claus redox system which react the hydrogen sulphide and sulphur dioxide from the front end furnace to produce elemental sulphur are critically temperature dependent. Earnie’s infra red thermometers might not have such a seminal role inside a catalyst bed, but they sure worked in keeping an IR eye on the external temperature gradients on the outside of the reactor bed. Catalyst activity drops off inside the charge and the heat of reaction drops and this can be detected on the outside shell. We have a problem inside; let’s fix it and keep the recovery up in the high nineties. Stands to reason. Oh that more of us humans had a better handle on this essential of all civilised activities – reasoning.
But there is still more about the role of temperature in the overall sulphur business. There are few if any other chemical elements that go through as many fundamental changes as sulphur in such a readily accessible temperature range. Its orthorhombic solid crystalline form ‘morphs’ to monoclinic before melting to liquid cyclooctasulphur at 119C. As it heats up to 159C its eight-membered ring molecules break up and reform into a variety of so called Sx species, and finally into long chain polymers which hugely affect its viscosity and fluidity. When it cools down again to solidify, all these species have to reverse themselves and do so at a variety of rates leading to very complex solid sulphur mixtures which can effect the handling and storage properties! Who said temperature control wasn’t a critical factor in the sulphur business?
Thank you, Earnie Emery for your contribution.
‘Thiophilos’
Is China running out of steam?
During 2010 we seem to have moved back into another commodity price boom, with all major commodities, from oil to metals, grains and of course sulphur all heading back to the kind of price levels last seen in 2007-8.
Much of the rise in markets has been sustained by activity in the developing world, especially China, where the economy surged forward last year. GDP has grown by 10.3% in 2010, up from 8.7% in 2009, with strongest growth in 4Q 2010 and projected to go forward into 1H 2011. The Chinese government has actually become concerned by the pace of growth and taken steps to try and throttle back the economy, raising the standards for bank lending seven times in an attempt to ease back the flow of credit, and it is forecast that interest rates may have to begin to rise soon. Some people in commodity markets have become concerned by this, saying that 2011 will be a year of “downside risks” and bear markets. Costs are rising in many commodity markets, they argue, as producers must pay for development costs in local currency but sell in dollars, a currency that has weakened against many currencies – especially the Chinese yuan - over the past two years. The fear is that the Chinese economy is trying to expand too quickly and will soon fall victim to its own success, bringing the current commodity boom down with it.
Needless to say, others take a different view and say that fiscal moves in China will merely prevent overheating, and that Chinese demand remains robust. Among the bears, Danske Bank’s 2011 Commodities Report argues that we are still on the upswing of a 40-year demand-driven ‘super-cycle’ in commodity markets which last peaked in the mid-1970s (driven in the 1950s - 70s, it was argued, by post-war economic growth in Europe and Japan, and finally curtailed by the Oil Crisis) and which hit its trough around the turn of the millennium as markets were flooded in the wake of the collapse of the FSU and Eastern European economies. Seen in these terms, it argues, 2008 was merely a short-term correction to a continuing prevailing upward trend, now driven by Chinese (and to a lesser extent Indian) industrialisation, which may not peak until some time between 2015 and 2025. The super-cycle was an idea which gained a good degree of popularity in commodity markets in the 2005-08 period, was quietly brushed aside during the recession, but seems to be gaining traction again.
Certainly the future for base metals appears to be tighter markets and higher prices. Copper in particular is singled out for more record pricing – probably topping $11,000/t. Stocks to consumption ratios on the London Metal Exchange are standing at a historical low of 2.3 weeks and deficits are, according to some commentators, becoming “structural”. On the agricultural side, too, while wheat is roughly in balance, there are low stocks on the corn side – just 16% of annual demand and well below the 20-40% range that is generally considered a balanced market.
The impact on sulphur is harder to predict, dependent as it is upon various other commodities. But as we discuss in Sulphur in this issue, China’s hunger for copper has led to a major increase in sulphuric acid production from smelting in the region, while the buoyant nickel market is gradually having the reverse effect by driving increased acid consumption in leaching projects. Record phosphate prices continue to feed into sulphur demand for agriculture, but high oil and gasoline prices have driven major investment in refining capacity and increased sulphur production. Overall the pressure seems to be on the upside rather than the downside, and China has certainly become an engine of the sulphur market – in 2009 it imported 12.1 million tonnes, and the figure for 2010 will probably be 10.0 – 10.5 million tonnes. Sulphuric acid production was up 20% over the year. So far this has sustained sulphur prices in the range $165-175/tonne, and producers around the world are presumably making hay. The indications seem to be that China’s boom has at least a few more years to run, even if its sustainability in the long run is more open to question.
Much of the rise in markets has been sustained by activity in the developing world, especially China, where the economy surged forward last year. GDP has grown by 10.3% in 2010, up from 8.7% in 2009, with strongest growth in 4Q 2010 and projected to go forward into 1H 2011. The Chinese government has actually become concerned by the pace of growth and taken steps to try and throttle back the economy, raising the standards for bank lending seven times in an attempt to ease back the flow of credit, and it is forecast that interest rates may have to begin to rise soon. Some people in commodity markets have become concerned by this, saying that 2011 will be a year of “downside risks” and bear markets. Costs are rising in many commodity markets, they argue, as producers must pay for development costs in local currency but sell in dollars, a currency that has weakened against many currencies – especially the Chinese yuan - over the past two years. The fear is that the Chinese economy is trying to expand too quickly and will soon fall victim to its own success, bringing the current commodity boom down with it.
Needless to say, others take a different view and say that fiscal moves in China will merely prevent overheating, and that Chinese demand remains robust. Among the bears, Danske Bank’s 2011 Commodities Report argues that we are still on the upswing of a 40-year demand-driven ‘super-cycle’ in commodity markets which last peaked in the mid-1970s (driven in the 1950s - 70s, it was argued, by post-war economic growth in Europe and Japan, and finally curtailed by the Oil Crisis) and which hit its trough around the turn of the millennium as markets were flooded in the wake of the collapse of the FSU and Eastern European economies. Seen in these terms, it argues, 2008 was merely a short-term correction to a continuing prevailing upward trend, now driven by Chinese (and to a lesser extent Indian) industrialisation, which may not peak until some time between 2015 and 2025. The super-cycle was an idea which gained a good degree of popularity in commodity markets in the 2005-08 period, was quietly brushed aside during the recession, but seems to be gaining traction again.
Certainly the future for base metals appears to be tighter markets and higher prices. Copper in particular is singled out for more record pricing – probably topping $11,000/t. Stocks to consumption ratios on the London Metal Exchange are standing at a historical low of 2.3 weeks and deficits are, according to some commentators, becoming “structural”. On the agricultural side, too, while wheat is roughly in balance, there are low stocks on the corn side – just 16% of annual demand and well below the 20-40% range that is generally considered a balanced market.
The impact on sulphur is harder to predict, dependent as it is upon various other commodities. But as we discuss in Sulphur in this issue, China’s hunger for copper has led to a major increase in sulphuric acid production from smelting in the region, while the buoyant nickel market is gradually having the reverse effect by driving increased acid consumption in leaching projects. Record phosphate prices continue to feed into sulphur demand for agriculture, but high oil and gasoline prices have driven major investment in refining capacity and increased sulphur production. Overall the pressure seems to be on the upside rather than the downside, and China has certainly become an engine of the sulphur market – in 2009 it imported 12.1 million tonnes, and the figure for 2010 will probably be 10.0 – 10.5 million tonnes. Sulphuric acid production was up 20% over the year. So far this has sustained sulphur prices in the range $165-175/tonne, and producers around the world are presumably making hay. The indications seem to be that China’s boom has at least a few more years to run, even if its sustainability in the long run is more open to question.
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