 So, hello and welcome to the recording of the ultimate analysis, which is also known as elemental analysis or elemental distribution and the proximate analysis as well. Notice the terminology is proximate, not aproximate, very different things. So basic cold quality, we cover a bunch of things and we're going to see all three of these components used together. We'll do calorific value at a later date. However, if we look at ultimate analysis, it's a combination of the primary elements, the carbon, hydrogen, nitrogen, the sulfur and the oxygen. They all have utility in that it's desirable to know what the values are because those values are used in decision-making. And that's what you're going to be doing is making decisions. The calorific value is also needed and that'll be a third experiment we will do. For the proximate analysis, it has four components, moisture, volatile matter, fixed carbon and ash. And so there is no ash in cold unless there might be some volcanic ash perhaps or some forest fire ash. But there is mineral matter that transforms into ash. And again, these have a great utility in determining the appropriate use for coal or other things. And of course, if you read a good book chapter, that'll be very evident. So in combination, we certainly look at environmental issues, certainly things like nitrogen and sulfur, even now carbon dioxide. There are trace metals as well, and for certain ranks of coal. And coal rank is a classification system. It is not a ranking. So we never discuss ranking and you discuss rank. So the classification system is very helpful in getting like behaving coals into the same sort of classification bins. And so certain of the coals are also used in cook-making and those can be considerably more valuable. So, basic coal quality. So one of the things that we'll get to later in the course is about getting a representative sample. There are multiple approaches to sample from coal. When I've gone into mines, we have done the full-seam channel sample for the coal sample bank that we have here. Sometimes might get a core sample. Column samples are very difficult to obtain, very expensive and challenging. But a channel sample of a lithotype perhaps might be doable, or even perhaps a column sample of a lithotype. So this is a banded coal. It's probably a tumulus coal and we see multiple horizontal layers. Those coals from each layer are going to be somewhat different. And so when you mine the seam, you're going to get different quality of material. Now there might be a seam above it, might be a seam below it. And so my quality might change as we continue the mining process. And so knowing these factors is very important. And so you need to get a representative sample for the analysis otherwise it's problematic. The ASTM International has multiple, this is just four examples, selecting from a truck, from a rail car, et cetera, et cetera. And so these are procedures which have to be appropriately done in the right order, the right equipment, in the right manner to get these representative samples. We're also going to go down and later in the course and talk about the combination process and getting down to using rifflers and crushing to get down to smaller particles, coating and quartering, things like that, to take a large amount of material to then get a smaller representative amount of material that we can do the analysis on. Our analysis typically done, or ASTM requirements is minus 60 mesh. And if you don't know what that is from your earlier courses, you should look it up and we'll discuss it later. So here's a good visual of proximate analysis. You can see the low rank coals are over here in yellow and greens. So the yellow would be the lignite, the green would be subbytuminous and you move over into the two minus and anthracite. I'm not sure what the red one is for a little volatile bituminous for some reason. You can see the low rank coals have a considerable amount of moisture, there are some coals in Australia that have more water in them than coal, and so by an American definition would not be coal. It would be water contaminated, coal I guess. We don't have lignites that are 50% water as shown here very often. It's closer to 30%, 34% might be high. But the moisture declines as you transition in the rank range. Again the ability to hold that water is lost during the coalification process and there's compression pushing it out as well. Volatile matter of course is variable so this is everything adds up to 100%. So the volatile matter yield here may only appear to be a little less than 20%, but if we were to dry the coal we would get considerably more. So you can see that the volatile yields tend to decrease, they're very low in anthracites, very difficult to ignite them, and as we can see the transition in fixed carbon going up as well. Notice that we are not showing the mineral matter or the ash yield and so this is on a mineral matter free basis. It's very important to always tell me when you're discussing coal what basis it's actually on for us to make logical decisions. We don't put that in rank because the amount of mineral matter in a coal is dependent on depositional environment and other aspects and it's unrelated really to the coal forming process. There are some exceptions, mineralization in the cleat system etc etc, but it's just very variable and it's not part of the organic component of the coal. I know Sarah, but you put the sources being the USGS, it's not really enough information to find that, so I really should have put the title of that resource as well. So put your resources down when you do presentations, your sources of information. Don't use a URL because that doesn't give me an indication of quality. If you know that USGS is the United States Geological Survey, you know that's a very reputable resource to use for coal. So here's the calorific value. So the energy content is a very low level way of saying things. It really isn't an energy content because the physicists would get upset, not that I'm opposed to upsetting physicists, but it's not really energy content. It's the energy released through the combustion process, or perhaps gasification etc etc. But if you do the combustion in oxygen, you can see that we have a very variable calorific value. It increases until we hit low volatile but humanist coal as a transition point and then decreases. It's increasing here because we are losing oxygen from the structure of the coal and a few other things. And so the carbon content is becoming concentrated as well as a little bit of hydrogen content and it declines because of lots of hydrogen in the formation of the anthracites. And so we can use this value to cluster the coals to get a sense of how well they behave, but we can only do it up until about this mark here, 14,000 BTUs because above that we can't really tell the rank. So how do we know the rank? Well, this is from ASTM International, it's D388. I haven't supplied you with this, I don't think, and so we should go and look it up. And you can see that there's two ways of determining rank. You can look at the fixed carbon or the volatile matter. If you do that, it's on a dry and mineral matter, a dry but mineral matter free basis or the volatile matter. And then we can, for the higher rank coals, we can determine the rank for values less than that 14,000 BTUs. And that's on a moisture containing mineral matter free basis because moisture obviously has a role to play in the difference between gross and net calorific value. Notice that also we're not just discussing anthracites, petuminous, sub-petuminous, and lignite, that there are subclassifications. Again, that has implications for how the coal is used, and you need to look into some books to determine how that is. So here's a good example, putting the source appropriately, ASTM International D388. The STASH17 tells me that was released in or re-released in the year 2017, and the title of the standard. Again, every coal is unique. This is a van Krevelen diagram, the atomic H2C ratio versus the atomic O2C ratio. And you can see as you start off the lignite, it's got quite a broad span. Throughout the qualification process, you tend to be losing oxygen. And then a little later, the higher ranks, you tend to lose a little bit more hydrogen. There is considerable spread. Every coal is unique. But we like to have an idea of how it will behave, and that's why we do a classification system called rank. Again, not ranking, but rank. So discuss coal rank. I would refer to the lignite and the sub-petuminous region as low rank, so low hyphen rank. And this is the petuminous nanothera side as high rank, so high hyphen rank. So a lot of hyphens in the low hyphen, low volatile, sorry, low hyphen volatile, the two minus culls, or the high hyphen volatile petuminous culls. And again, there are sub classifications for very good reason. You need to work out why. So how does things like caloric value in sulfur get used? Here's one of the older rules now. We're in a position of transitioning this to even lower values. But we were allowed 1.2 pounds of sulfur dioxide per million BTUs. It was restricted to some of the larger entities. And so if you're mining coal from northern Appalachians close to us, you have to do something to get it below this line, and you have choices. Or of course you can move and perhaps use some powder of basin coal instead, because it has lower sulfur, but it also has a lower caloric value. So you need to buy more of it. Now this stuff is cheap. This stuff is rather inexpensive. But there are restrictions to end the design of the boiler for what you can do. There's a lot more regulations now regarding the smaller and smaller units for being in compliance with our lower sulfur emissions. And this choice isn't how to get there. So it's not just about how much sulfur is in coal. It depends also on what that caloric value is. So heterotoms. Oxygen, it lowers your caloric value. If your coal gets oxidized by sitting out in the weather in the rain, it will impact your coking properties. It impacts your water holding ability through hydrogen bonding. Obviously we get oxygen from the plant material. So biomass is actually quite oxygen rich. And obviously from your combustion course, you know that we like to use the oxygen content for the excess calculations as well. And generally as you increase the carbon content, there is a pretty much linear reduction in the oxygen content. Nitrogen is obviously going to give you knocks to some degree. It's not 100%. Some of the nitrogen gets retained. Some of it gets converted to other things. It doesn't vary a lot with rank. It varies a little bit more with the biomass inputs and things like that. You don't tend to select coal based on nitrogen values like you do on sulfur. Sulfur, of course, is going to give you sulfur dioxide emissions. Obviously both sulfur and knocks contribute to the acid depositional challenges. Sulfur is more complicated because it's both organic and inorganic. And so things like pyrite as well as sulfur being in things like dipensifurand type of structures. There's not a lot of sulfur in much of the biomass that we typically use, but sulfur-based bacteria in the depositional process, so in the bogs, can cause increases and then C as well have higher sulfur levels. If we're talking about fuel, we now have low diesel sulfur. The diesel was helpful for lubricity, but now you have to do different things. Anyway, so the heterotoms are important for emissions and for behaviors. There are a whole bunch of conversions and corrections when we do elemental analysis to convert things from an as-received to a dry basis. Obviously, if you're looking at hydrogen, you get some contribution from hydrogen from the water that's not the hydrogen in the coal structure itself. It's in the water in the structure, and so obviously oxygen is much higher molecular weight or atomic mass than hydrogen, so that's where this 0.119 comes from. And so there are various corrections that you need to do to the data because when we do the combustion process to get the yield of products that we analyze, the mass that we weigh isn't pure coal. It contains mineral matter and perhaps moisture, and so there's a lot of conversions and corrections that are necessary for the exam. You need to know how instruments work as well as how to why corrections are done and to do the corrections for the report. Here's an example of one of our elemental analysis. This is the liqueur which is about to be replaced because it keeps dying. You can see there's two components. There's the CHN components on the left and the sulfur analysis on the right. This is just the higher furnace temperature is the reason why. Now, this is taken directly from... I don't think it's from the SEM. I think it's the instrument manufacturer's site. But do not copy and paste the quotations in your report. It's unacceptable. You need to rewrite these things and obviously cite the source. So what do we have here? This is the sample loading location. A known mass for decimal places gets put in a tin cup or an aluminium foil sort of ball. The system goes through a whole bunch of purges. We do a whole bunch of blank runs necessary to sweep nitrogen from air out of the system, make sure all the sensors are up to temperature, make sure the oven is at the right temperature. We run in a few blanks depending on how long the system's been sitting without a run. And it background values the things like nitrogen coming down until acceptable values. So it's not really a blank. We don't do a correction. We just really do that as a means of conditioning the instrument, but it's called a blank in the system. There's a primary furnace at 950 and an after burner furnace at 850 degrees C. We use ultra-high purity oxygen. And so once the system has been flushed with helium, we have oxygen flush with helium. The sample drops onto a tray. The system continually flushes with helium to get rid of the air that we just got introduced. And then when the system is ready to go, that shelf retracts. The sample falls down into the primary furnace. We have a combustion process. We get complete combustion by going through the after burner. We do have some other complex controls that we can change how the flow of oxygen happens, if things are particularly difficult to burn, or if they're easy by biomass, we can slow down the flow and things like that. That's a bit of a detail. You can't just look at the first bit of gases coming off. It's very different from the last gases coming off because the volatiles are combusting than the char is combusting. And so all of that material is collected in something known as a ballast. A coffee cup, a coffee can sized piece of apparatus. When things have reached the equilibrium and so the combustion process is finished, then small portions go to infrared detectors. Take about three ccs. And we do infrared. This will be a Lambert law for carbon dioxide and water. Nitrogen oxides do not all have infrared stretches and bends and writings, et cetera. Only some of them, those molecules. And so NOx gets converted back to nitrogen. And so it goes through a reduction location, a reduction furnace with copper. And we use thermal conductivity to determine the nitrogen. For the sulfur, we do a different furnace. I think I have a slide later. So minus 60 mesh sample. Infrared for CO2. Infrared for H2O. Thermal conductivity nitrogen. Sulfur is also done by infrared. There instead of doing a ballast collection, it's an integration over time over the collection of the data. Oxygen is determined by difference. So this means that there's uncertainty in all of these, but there's greater uncertainty in the oxygen propagation of errors. And of course, if we're making decision on things like the sulfur content, then we need to know what the uncertainty is or the variability potentially in that data. And so part of what you do is you're going to collect data, you're going to manipulate it, you're going to correct it, you're going to present it in a manner that makes sense to communicate your decision making process. And part of that is knowing uncertainties. So read the STM. It's very helpful. So conditioning runs, moves there, before we do anything else. We have to do calibrations. We want to use a calibration that's close to the carbon content of the material you're using. So maybe a different calibration if you're using char or coke, then you would for a low rank coal. And so we do a, take a number of known values. So we can talk about accuracy when we know particular values. And so we can set up a graph that shows this is the content and this is the response factor for carbon, for example, or sulfur. And we do that over time. The values change a little bit. And so one of the things you do is put in a known sample. And you do that, say every 10th sample or so. And you can look over time to see how that value changes and you can correct the drift, which is essentially just moving the calibration line down a little bit to get back to the correct value. Because calibration takes the whole day. So just doing a slight drift correction is relatively small. So sample again minus 60 mesh. You may dry it prior to or you may not, but you need to know what that moisture value is. You need to know what the ash yield is or the mineral matter value. And so we know the sample mass to four decimal places. And it goes through the burn profile for combustion. So here's an example of how hydrogen content might be used. This is Silas chart. And so you have this band of how the coal behaves. Again, this would be a low rank coal. This would be a high rank coal. You can also get a sense that you can also plot the oxygen transition here as well. And from the carbon content or from the hydrogen content, you can get a sense what the carbon content is. You can get a sense of where in the classification scheme or the behaviors that the coal will fall. Notice that this is given on a dry mineral matter free basis. Always tell me the basis otherwise you will get yelled at. We can do things like predict the higher heating value from the carbon hydrogen oxygen sulfur content with a correction for the ash yield. So a whole bunch of things that you can do and be predictive if you knew what the elemental composition is. Moving on to Proxman analysis. This is a glorified oven. We flow nitrogen through it. There is a crucible and it has a cover. If you say there's a cup and a lid, I know that you haven't read the ASTM or that you're not next word or because you're not using the lexicon of the field. And so use the right terminology. It has a particular shape to it. It's very specific and there's a reason for that as well as having a cover. I don't think the cover is necessary anymore, but I think it's still there. It's a historical holdover. Perhaps there are a few coals, cooking coals particularly perhaps where it might be helpful. So glorified oven. If you look inside you'll see we've got all these crucibles. One crucible will be very clean. It's in the first position and that's just a way continually throughout the process and it allows us to know what the constant weight is, the temperature and the oven changes. And so we do typically typical analysis. Sometimes more we do that for elemental analysis as well. Remember it's important to know uncertainty and there's one balance here and so essentially this carousel rotates and it weighs each crucible. So you weigh it when it's empty. You add sample which is typically around one gram. Again we know the value to four decimal places from the balance. There is precision and accuracy in the balance which is important. And once the crucibles are all been weighed we know what the mass is in triplet analysis typically. Perhaps more. The oven then goes into a heating mode. There are some desirable heating rates that's listed in the STM. And as nitrogen flows in and it has to exchange the volume of the oven a certain times number of times per minute. Again take a look at the STM. We continue anyway until we get no significant mass change. And as we've heated up to 105 degrees there's a range I think you're allowed. About 105 degrees Celsius. Then you can determine what that mass is. So moisture. So once you've got the moisture the lid goes on and so that whole process the cover I'm sorry goes on. The lid of the instrument opens up allows you to put in the cover with the tongs. The oven lid when closes. It's heated up to a temperature of 950 degrees Celsius I think. And typically that would be done for seven minutes. I say with lids I really should say with covers to get that right. Again it's in a note atmosphere we're looking at what material come off. So don't talk about volatile matter content. You should talk about volatile matter yield. Once that occurs then it cools down to about 600-700 degrees Celsius. The lid of the instrument will open. This allows us to remove the cover and allows then the lid of the instrument to close. The oven is heated back up to 750 degrees Celsius. The gas then changes to oxygen and we remove the leftover fixed carbon leaving the ash behind and so we generate an ash yield. And from those three values we can determine the fixed carbon by difference. So this is typical data that we'll give you. We have the initial mass that this is the mass after the moisture has been lost. And so it's the difference. I think the rest are actual direct measure masses. Check with the TA when you're in the lab. And you can see we've got multiple analyses and you each work with a different dataset. So do take a look at that. I've only talked about coal but we do the same thing with biomass. Biomass is obviously used as an energy generation fuel. Typically biomass waste although sometimes we're now deliberately growing biomass to be a fuel. And so it's applicable for both coal and biomass and biomass pellets and things like that. And then perhaps the mixtures. Again there are corrections. We have a desire to know what things are on different bases. So sometimes we'll talk about as received. Sometimes we'll do dry, dry ash free. And so this is just like saying in a classroom of 30 students if 10 of them were female then on a male student basis there would be 20. It's nothing more complex than doing some simple calculations along those lines. But we need to know what the basis is. If I ask you how many students there are you don't know the answer because am I talking about in the Pennsylvania state system? Are we talking about in University Park? In the incoming freshman class in energy engineering? Or in room 220 Hammond on a Tuesday you know the 2nd of September? And so I need to know what students were talking about and so I need to know the basis. And it's exactly the same when we talk about values. So is it fixed carbon? Does it include a contribution from moisture or is it not? Etc. Etc. So is it as received? Is it dry? Is it a dry mineral matter free basis? The mineral matter goes through some interesting transformations and so it is not the same value as the ash. Some minerals gain weight, a mass, some minerals lose mass. And so you need to know some things like that. So where's the lab and what time? We do a staggered start so please go and take a look at the sign-in sheet. Might well be in Canvas if you're looking at this lecture online. Obviously you need to dress appropriately so it's long pants, it's clothes, toe shoes, with socks. I don't want to see exposed skin. Again it's the standard behavior in industry. We're going to give you a lab coat and glasses. Put the glasses on immediately as you enter or you'll get poked in the eye. Don't have hats. Again it's a fire risk. I know chewing gum it's a poisoning risk and if you chew gum I will poison you so that's a double enhanced risk. And no food or drink because again you'll die. Approximately analysis we're going to obviously have hot surfaces and so be careful when dealing with the covers and there's a potential crush injury or impingement injury so when the lid closes on the oven. So that's it. Thank you very much.