81 comments on Refining 101: The Assay Essay
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81 comments on Refining 101: The Assay Essay
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Very informative and nicely done.
Maybe you're planning on getting into this topic in one of your subsequent refinery essays, but I'd like to see some discussion on the final disposition of all the sulfur that is removed from the crude. Even at less than 1% of the crude, it has to be a truly huge amount of material, and will become even larger as more and more 3%-sulfur heavy crude is used.
If I recall correctly, there are several pathways for the sulfur that is removed: i) combustion of H2S and discharge of SO2 air emissions, ii) removal of SO2 from i) as calcium sulfate sludge, iii) conversion to sulfuric acid, and iv) removal as elemental sulfur. I'd be interested to know which is the most common pathway at present.
It would seem to me that if high-sulfur heavy crude is going to constitute an increasing fraction of a refinery's imput, then the disposition of the removed sulfur is going to become increasingly problematic, giving that there appears (last time I looked) to be a glut of byproduct sulfuric acid and elemental sulfur.
In at least some cases, it ends up as elemental sulphur. I saw a picture once of a giant yellow mountain of the stuff. Not sure, but I think it was next to the tar sands thing in Canada.
In at least some cases, it ends up as elemental sulphur.
That is the case with the plants I am familiar with. The removed H2S gets turned into elemental sulfur and sold. Emissions of things like SO2 are pretty strictly regulated in the U.S. (this wasn't always the case, though).
google Claus sulfur plants.
that's the typical refinery process.
http://www.ortloff.com/sulfur/claus.htm
Saudi was trying to use sulfur to make concrete like roads just to get rid of their huge excess.
First world refineries don't just put all the sulfur up the stacks as SOX.
What happens to the sulfur depends on economics. It's a pretty good bet that the price of elemental sulfur will continue to fall because sulfur is also piling up at coal-fired power plants while the demand for sulfur is not growing at anything like the same rate. In some cases, the sulfur can be made into sulfuric acid on site and sold as such, but in the long run that will just knock down the price of H2SO4. I expect elemental sulfur will eventual be treated as a waste.
When I was taking chemistry (about 3 decades ago), the professor mentioned that the price of H2SO4 as an industrial chemical was the cost of transportation from Texas Gulf Sulfur or wherever. The white vitriol in the lab was that price, plus the cost of the container.
I do recall seeing a picture of a sulfur mountain back then, produced by the Frasch Process. Is it even necessary to exploit sulfur deposits that way any more?
Bought some as soil adment spring 05. $5.50/50 lb sack. There are mountains of it off the AlCan, northern BC, back in late 90's.
According to legend, both rural and urban, there is a yellow pile in Khazahkstan that is visible from space, presumably with the naked eye, as the clothed one can see your lawn ornaments. Having seen trainloads of sulphur on their way from Alberta to Vancouver, I can imagine there are numerous piles there, too.
Apart from vulcanising rubber and such, I suspect the production vastly exceeds the demand. Sulphur burns all too well in a rather molten state, and was used to kindle coal fires, but that was before my time, or after, perhaps. I did get a lump fired up on my bench as a kid and it burned relentlessly, clear through two layers of 1/2" plywood before hitting the floor. I resolved to leave it alone, but all this sulphur must be going somewhere and the atmosphere is my guess.
It sure makes an impressive fuel, if no one is looking. Hot and cheap. Brimstone. Sulphur dioxide makes carbon dioxide look like a good guy. I would imagine that the shipping costs from the Caspian far exceed the value, but rolling it downhill from Alberta to a waiting barge should be about as cheap as rail maintenance. As to who gets the honor of 'utilising' it and how remains a mystery. I have often mused on this as the jaunty yellow trains roll by. And I remain fathful to the ph spelling 'cause it looks better, and mixed with water it has quite an effect on PH. Phew!
The US does not seem to have enough... we keep importing some:
http://minerals.usgs.gov/minerals/pubs/commodity/sulfur/640301.pdf
Most of the sufur probably ends up in the chemical industry first. Without sulfuric acid most basic synthesis chains would come to a halt. A lot, it seems, is needed in agriculture in fertilizers. I am not sure where it goes from there... in the end it will have to be bound in some organic or inorganic form and then be deposited geologically. I haven't been able to find out what the end products are... but it could very well be that the sulfur in coal and oil is an end product of a similar chemical reaction chain that produces current organic sediments.
One other product is modern soap, or SDS (sodium dodecyl sulfate). In this the two divorcees, petrol and sulfur, marry again...
Sulfur is not a long-term environmental problem. Though its compounds cause acute damage, being toxic, smelly, and corrosive in the immediate area of a spill, it will join the natural sulfur cycle fairly quickly. I'm not sure precisely how quickly, but the only sulfur compound I'm aware of that has a significant environmental half-life is SF6. Then there's acid rain — but that tends to stop when you stop emitting SO2. It isn't like heavy metals.
In an aerobic environment, it will exist as SO4-- ions, and in an anaerobic environment, it exists as S-- ions. Various wild sulfur-loving bacteria will perform the conversion for you. It also exists as biological sulfur; certain amino acids and small molecules present in living things everywhere contain sulfur atoms.
Bottom line is, your sulfur spill will find something to react with and become environmental sulfate. If it encounters calcium, you'll have gypsum. If it's in a stream it will end up in the ocean as sulfate. Since we aren't burning sulfur to keep warm (yet), not enough of it is being dumped/spilled/spewed to acidify the ocean.
A few years back when I was working at a Zinc Smelter that processed ZnS ores, we roasted the ZnS to make ZnO and SO2. The exhaust gases went through a series of cleanup steps followed by a series of 4 catalyst reactors(not cheap!) to turn to the SO2 into SO3. The SO3 was bubbled through H20 to make H2SO4.
This effectively reduced the stack SO2 from 7% to 150ppm, but the acid was basically sold at cost +/- a few $/MT. This was in Clarksville, TN.
IIRC we made ~250,000 MT /yr of 93-98% sulferic (about 20 semis full per day).