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blogfast25
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aga (and j_sum1):
The idea of oxidising organic nitrogen (read amines, amides and other mainly nitrogen/hydrogen MO bearing materials) to NOx with traditional
combustion methods is in fact beyond risible.
Way before the advent of the Haber and Ostwald processes wars were being fought over access to nitrate bearing resources:
http://en.wikipedia.org/wiki/War_of_the_Pacific
Do you really think no one would have thought of such a process already, considering it would make one as rich as Croesus in the case of success?
The N-O bond really doesn't form easily at all, see also the extraordinary forcing conditions applied in the Ostwald process.
Apart from the combination of N2 and O2 to NOx in an electrical arc, the only avenue worth investigating is the microbiological digestion of
ammoniacal nitrogen to nitrates.
[Edited on 30-1-2015 by blogfast25]
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j_sum1
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Better add deltaH to your list there blogfast.
I have to say that I really respect your thoughts and your knowledge base which well and truly eclipses mine. But it won't stop me experimenting and
exploring some ideas for myself. Risible is a strong word.
I was thinking along the lines of the Ostwald process and then was daunted by the pressure requirements and the necessity to divert some of the stream
back through the reactor. And that is before attempting to find some otc platinum that met the brief. I was also thinking along the lines of urea
and milk protein as a starting material when deltaH suggested soy beans. I have not found any online evidence of anyone attempting this kind of
process so it will either be a dismal failure as you predict or a novel method.
I think I have said a number of times that I don't consider myself a particularly competent competitor in this challenge. But I do love the
experimental process -- enough to post what I considered a failure. I was genuinely stunned to be even considered for a prize. Given that I didn't
get to see what I hoped, I am going to continue the experiment.
There is another possible route that has some similarities to mine and might be extremely simple. I am not going to attempt it but I offer it out
there to be picked up by someone.
Why not rip the catalytic converter off your car and bubble the exhaust gases through water. That should produce something (or else what is the
catalytic converter for?) I don't think the nitric acid would necessarily be cheap by this method. But the process would be simple and the necessary
equipment ubiquitous.
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blogfast25
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Nothing wrong with 'strong' words at all.
The idea that in this day and age and with the power of so much hindsight some would still entertain the idea of 'burning' (let's call a spade a
spade) nitrogenous matter to nitrogen oxides just baffles me.
Had those entertaining that idea made it conditional to the use of some 'catalyst X' it would have gained minimum credibility in my eyes, even in the
light of the enormous difficulty of developing/deploying such pixiedust. But that seems to have crossed no one's mind either (apologies if I've missed
that part).
[Edited on 31-1-2015 by blogfast25]
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j_sum1
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You are far more knowledgeable than I am -- both historically and chemically. You have the benefit of a lot more hindsight. And I am not aat all
offended that you should choose strong words.
I can see that I am going to find out what it is about burning hydrocarbons in air at pressure that causes some N2 to oxidise.
Admittedly without any significant thermodynamic research I blended ideas about oxidising N2 in a combustion engine and oxidising NH3 in the Ostwald
process and wondered what would happen if one attempted oxidation of urea or proteins.
I am more than open to the idea of catalysis but have no experience in selecting an appropriate catalyst.
And if you can point me to some thermodynamic data that indicates that it really is infeasible then I would welcome it. (In which case no catalyst is
going to help anyway.) But I sure wouldn't ask you to do my research for me.
In the meantime, I am happy to put a bit of time into reading and have a couple of modifications that I would like to try. It sure can't hurt.
Worst case scenario is that I buy some peanuts and end up making them into cookies.
[edit]
Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?
[Edited on 31-1-2015 by j_sum1]
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Zombie
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Can you make enough for all of us? 
They tried to have me "put to sleep" so I came back to return the favor.
Zom.
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plante1999
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I'm on blogfast side here and I actually worked a bunch on this mater and put a lot of my money (and investor money) in the search for something
viable and I have gained a fair amount of knowledge on the subject.
Like I said early in this thread, without quartz tube and or high voltage you are only going to piss in a dirt pile. Seriously, nitrates where a very
rare material when it gained large use in Energetic and bullet propellant manufacture. Actually, the ONLY reason Germany was able to go in war was by
inventing the Ostwald process. Arc process do work and is not that costly for amateur, but in industrial scale it is not worth it.
The point I'm making is that if there was another catalyst then platinum (which is already hard to work with), it would have gained mainstream
industrial use.
Also, nitrogen is extremely unlikely to get oxidized, and thinking the mere burning of nitrogen material at atmospheric pressure without catalyst is
beyond my understanding. Engines yield some NOx because of the extreme pressure and temperature, plus the radicals present during engine run (not to
mention some metal oxide catalyst).
I would be A LOT more entertained to see the same exact challenge with allowed quartz tubing, platinum wire and or high voltage.
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Zombie
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http://www.ebay.com/itm/2-lb-Sodium-Nitrate-Gold-Scrap-Refin...
http://www.ebay.com/itm/Sulfuric-Acid-98-1000Ml-Poly-Bottle-...
[Edited on 31-1-2015 by Zombie]
They tried to have me "put to sleep" so I came back to return the favor.
Zom.
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j_sum1
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Right back at you zombie.
I think it was established fairly early on and clarified by aga that use of commercial nitrates was outside of the parameters of the competition. And
I have pointed out a couple of times that they are not universally available anyway.
I am interested in what Plante1999 and blogfast have to say. Early on in the thread there was much vocalising of "it's impossible". Now there is a
bit more "It's impossible because..."
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Zombie
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Not to bust stones here. It's your game fellas... Some guys can't get the acid, some guys can't get the nitrates, some guys can't get iron lungs for
pressure, some can't get bat poo, Burning beans, and car exhaust are just not quick / easy, and No one want to ferment pee.
In essence it is a great exorcise for the brain but the reality is if two guys teamed up, and exchanged what they have... Cookie time.
I mean no offense, It just seems to outlandish to climb a mountain for a snow flake.
In MY humble opinion... The fella that burnt the beans won because he was the only fella to submit. The rest is all split milk, and soggy cookies.
They tried to have me "put to sleep" so I came back to return the favor.
Zom.
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j_sum1
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It sure is. It is and always has been a competition and a challenge. Playing is optional. Constructive evaluation of ideas presented is welcome.
Criticism of the competition parameters is less so.
Mallory reportedly said when asked why he climbed mountains, "Because it is there." As one who also has a passion for mountaineering, I share the
sentiment. It is more about the journey than the destination.
In terms of this thread, I have learned a lot about nitric acid and its production that I would never have known if I hadn't participated. For me it
was always about the learning, about having a project for my new lab and the possible bonus of someone unearthing a cheap and simple otc source of a
useful reagent. Even if that bonus proves elusive or impossible, it has been a worthwhile exercise.
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deltaH
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The attached paper studies the combustion of urea-formaldehyde re-inforced chipboard and investigates the use of air staging to lower the amount of
NOx produced.[1]
This paper is interesting, because while wood doesn't contain much protein and hence nitrogenic matter, the urea-formaldehyde raises the nitrogen
content to 3.58%, resulting in a big 'problem'  of making NOx during combustion.
The theoretical maximum amount being some 12300ppm NOx as NO2, according to the paper.
If you look at figure 9 in the paper, you see that using a stoichiometric ratio of air above 2.5 when burning UF-chipboard results in a NOx content of
a little over 1000ppm in their furnace... that's not too shabby.
No catalyst, no forcing conditions.
I suggest that it would be wise to pump ice water (perhaps in a closed loop from container with ice) through the absorber to maximise the
stripping of NOx and concentration of the nitric acid that is ultimately yielded.
Still prefer soybeans though...
Blogfast, I quote from the introduction of the attached paper:
| Quote: | | The NOx emissions from biomass combustion are mainly caused by the nitrogen in the fuel.[2] |
As for the why hasn't this been done before, quite simply because it doesn't work as well as burning ammonia over platinum (far from it),
nevertheless, in the amateur context, it might work well enough.
As for the catalyst, I've already discussed it to death in aga's thread about ammonia oxidation, as well as suggestions for upping
the activity of copper pixie dust  If one were inclined to incorporate a catalyst
with bean burning, I'd suggest soaking the beans in a copper salt solution overnight to absorb (preferably not sulfate), then drying them in the sun.
It's a complication and extra expense though...
Attachment: fuelstaging.pdf (243kB)
This file has been downloaded 2051 times
References:
[1] Salzmann, R. (2001). Fuel Staging for NOx Reduction in Biomass Combustion: Experiments and Modeling. Energy & Fuels.
15, pp. 575-582.
[2] Nussbaumer, T. (1989). Schadstoffbildung bei der Verbrennung von Holz. Ph.D. Thesis ETH No. 8838.
[Edited on 31-1-2015 by deltaH]
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deltaH
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According to the wiki on Schweizer's reagent, air can oxidise the copper tetraamine complex to ammonium nitrites (references copy pasta'ed from the
article) at ?ambient conditions?  I found this intriguing. So far I've only
seen 'exotic' reagents affect ammonia oxidation under mild conditions. We've seen copper discussed as a heterogeneous catalyst for this reaction, so
here's the homogeneous version as well.
References:
Y. Cudennec, et al. (1995). "Etude cinétique de l'oxydation de l'ammoniac en présence d'ions cuivriques". Comptes Rendus Académie Sciences Paris,
série II,Méca; phys. chim. astron. 320(6): 309–316.
Y. Cudennec, et al. (1993). "Synthesis and study of Cu(NO2)2(NH3)4 and Cu(NO2)2(NH3)2". European journal of solid state and inorganic chemistry.
30(1-2): 77–85.
[Edited on 31-1-2015 by deltaH]
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CuReUS
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Quote: Originally posted by j_sum1  |
Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?
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depends on how you combust it
http://en.wikipedia.org/wiki/Dumas_method
http://en.wikipedia.org/wiki/Kjeldahl_method
what about my idea of burning melamine instead of beans.I am sure melamine contains more nitrogen pound per pound compared to beans
WGTR's arc method is the best,but the voltage input for that machine is going to be a limiting factor
if too high voltage is needed,the person who is running the machine might get raided by the cops,thinking that the person might be a drug cook
mallory ,do you mean keith mallory,from guns of navarone by alistair MacLean
http://en.wikipedia.org/wiki/The_Guns_of_Navarone_(novel)#Pl...
I thought he was a fictitious character
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j_sum1
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Mallory
http://en.wikipedia.org/wiki/George_Mallory
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deltaH
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Melamine powder? It's really hard to burn. Hexamine containing fuel tablets on the other hand...
The main reason I went with the 'crazy' idea of using soy is that its (1)really cheap, (2) available in most countries and (3), nobody would bat an
eyelid if you buy 20kg of it... hell you can buy 100kg (4)renewable.
Also, while the yield would probably be piss poor, if you build a 'rig' you could probably burn a lot quite quickly if you use a blower... which you
should anyhow to get decent excess air in there.
The absorber could be more of a challenge than the combustion chamber I think. For one thing and also as j_sum suggested, volumetric
flow rates are large and this can entrain the droplets significantly.
A packed absorber with random packing would work much better. Liquid needs to be pumped to the top and would trickle down. You use a wide range of
small objects as random packing, no need for the sophisticated shapes used by industry. The idea is simply to have a film of liquid falling over
objects where the objects increase the area of the film per volume of the absorber. The 'objects' need to be inert to the liquid and spread the
falling film out nicely.
[Edited on 31-1-2015 by deltaH]
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Loptr
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I just got a quote of $30 for a 23mm OD, 20mm ID, 300mm L Quartz test tube.
Not too expensive and can be shipped anywhere in the world.
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blogfast25
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| Quote: Originally posted by j_sum1 | Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?
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I honestly don't know. A mixture of organics like nitriles et al, ammonia, some nitrogen and probably very small amounts of NOx, if I had to guess...
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Etaoin Shrdlu
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| Quote: Originally posted by blogfast25 | | Quote: Originally posted by j_sum1 | Blogfast, do you mind telling me what you think does happen to the nitrogen in proteins when they are combusted?
|
I honestly don't know. A mixture of organics like nitriles et al, ammonia, some nitrogen and probably very small amounts of NOx, if I had to guess...
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Apparently amines do form NOx when burned. http://cameochemicals.noaa.gov/react/7
I can't find much on this, probably hampered by the fact that most of my searches are turning up information on using amines to treat combustion
gases.
EDIT: Source for ammonia. http://www.fs.fed.us/psw/publications/riggan/psw_1988_riggan...
Best source on fuel nitrogen conversion I can find for higher nitrogen content. https://books.google.com/books?id=tZYfa7vCJ_AC&lpg=PA93&...
[Edited on 1-31-2015 by Etaoin Shrdlu]
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aga
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| Quote: Originally posted by Loptr | I just got a quote of $30 for a 23mm OD, 20mm ID, 300mm L Quartz test tube.
Not too expensive and can be shipped anywhere in the world. |
It's more about lateral thinking really.
Try to imagine ways that you could make HNO3 on a desert island for example.
No electricity, no ebay, internet ... yet plenty of sunshine and saltwater.
And fish. Lots and lots of fish.
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deltaH
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Dry fish in sunshine then burn fish. Absorb NOx in seawater, then distil with solar still and more sunshine. Enjoy pina colada from coconut shell.
[Edited on 31-1-2015 by deltaH]
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blogfast25
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| Quote: | | The combustion of amines yields noxious NOx gases. |
Doesn't say much about yield though, does it?
Here's someone preparing cadaverine, a diamine. Doesn't look too hard. Burn and lets see?
http://www.sciencemadness.org/talk/viewthread.php?tid=61305
[Edited on 31-1-2015 by blogfast25]
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aga
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Does not Experimentation yield data ?
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blogfast25
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Specifically what experimentation are you referring to here?
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blogfast25
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Going by one of Etaoin's links, chances are that much of the burnt organic N will be found in the ashes... as ammonium salts. Provided incineration
temperatures aren't excessive. Quite a bit will escape as NH3.
[Edited on 1-2-2015 by blogfast25]
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radiance88
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There seems to be two sides here in this thread - those who think it can be done, and try (even if the yield is inefficient), and those who think that
it's impossible, and are persistent in telling us it's pointless for even trying for this goal.
The naysayers could be technically correct, and maybe in truth we really are screwed here and just spinning our wheels.
But personally, I'd rather see a bunch of novel attempts along with their write-ups, than to see everyone lose enthusiasm and heart over it and stop
trying, and let it go dead.
As a hobbyist, I've never seen this kind of ingenuity before, and it makes me a little bit excited to even see what people manage to come up with.
Watching people do this on YouTube was what inspired me to get into this and start studying in the first place.
Sure - you can buy plaster at the hardware store for much cheaper than what it costs you to make it via calcium chloride and magnesium sulfate - but
that's not entirely the point why someone does this at home.
Another reality here is we're not all here a bunch of pro chemists working in corporate labs, able to order any chemical we want to. We're a group of
people working each in his own way, attempting to cope with the societal, legal and economical constraints in our own environments, to practice
science as a hobby at home.
We can't always beat these said constraints - but we really don't have any choice but to keep on trying.
It's a challenge that obviously has amateur experimentalism at heart. It's fun and inspiring to see some folks just rig up something in their garage
or backyard even if they don't hit the mark. For some folks it's impossible and for some it's just another fun challenge that gives them something to
tinker around and have fun with.
I'd say let's see where this little road takes us, and just enjoy ourselves along the way.
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