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Author: Subject: Series of ETN nitration problems
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[*] posted on 27-5-2018 at 08:01
Series of ETN nitration problems


Lately i am encountering lots of problems trying to make some ETN. I did not have any issues in the past. My used to yields was about 50-60% which is ok for ETN and i was still satisfied with it, but lately i can not make any ETN at all. I was using H2SO4/AN. (100ml H2SO4, 50g AN or 65g kno3, 15g E)


I had some h2so4 left over from the past and i did tried to nitrate some. I did got some ETN maybe like 30-40% yields which is ok using kno3. i used kno3 cause i got some problems with AN. AN did not dissolved for some reason into H2SO4,and after nitration, when i crashed it into a water, the salt was there, i had to squeeze with my fingers in order to be dissolved into water, but was not like that before nitration. AN was recrystallized from fertilizer and that it what i used before with no problems at all. I was thinking that AN now contains some stuff that prevents nitration. After that i did not tried with AN again and i moved to kno3. Erythritol, kno3 and AN are always stored into a desiccator bag. My h2so4 usually comes from concentrating battery acid to azeotrope.

After those 2 nitration (1st failed with AN and the 2nd with kno3) i was out of H2SO4 so i would have to make some more. When i got some new H2SO4 i tried again with Kno3 2 times and i got 0 yields. I thought that my H2SO4 was the problem, i thought that i did not boiled it enough, so i boiled it more to be sure that it was concentrated. (Ofc everything done with proper safety and safety equipment.) After the 2nd concentration i tried again and i got 0 yields again. I have tried it with various temperatures too (from 10 to 40) with 0 yields always.

Some notes: When i am using kno3, almost at the end of the nitration, after adding my E, some N02 gas comes out, that was happened even at the 1st time i tried with kno3 when i did got some ETN. That was not happened with AN.

After the addition of kno3 the mixture does not look so strong as it did not fumed that much (fuming nitric acid), while in the past it did.

I have my E for like 4-5 years now, is it an issue? (i think not cause i did got some ETN with the 1st nitration)

It looks like the new H2SO4 is the problem right ? but i really dunno why. I can not see any reason why it does not working any more while in the past it did with no problems at all.

Also why AN does not dissolved into H2SO4 while in the past it was ok ?

Sorry for the big post but i really want to explain what is going on here.
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joseph6355
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[*] posted on 29-5-2018 at 20:46


Are you sure that you have ammonium nitrate instead of that calcium-ammonium nitrate fertilizer?
https://en.wikipedia.org/wiki/Calcium_ammonium_nitrate

Regarding the NO2 gases, is your temperature closely monitored? Are you using efficient stirring to prevent hot spots? ETN nitration carried by nitrate/H2SO4 process can form a very thick slurry, which would increase the chances of a runaway or hot spot formations. Thats why I'd rather nitrate ETN with Nitric Acid instead of a nitrating salt.
I leave the nitrating salts for picric acid. :P

Anyway, you could make 2 separate solutions, one for the ETN sulfates and other for the nitrating salt/H2SO4, and then you add the latter to the ETN sulfate one. This would allow your nitrate salt solution to be warmed in a hotplate, helping it to dissolve, just dont let it get too hot or nitric acid might boil away.




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[*] posted on 30-5-2018 at 11:28


I have tried it before and dissolving erythritol into h2so4 dropped my yields.

According to calcium-ammonium nitrate fertilizer maybe you have right. Is there any way to check if your AN contains calcium nitrate ? I checked the solubility of CaNO3 and it is almost the same as AN and it is like the same hygroscopic too.
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[*] posted on 30-5-2018 at 22:47


Quote: Originally posted by underground  
I have tried it before and dissolving erythritol into h2so4 dropped my yields.

According to calcium-ammonium nitrate fertilizer maybe you have right. Is there any way to check if your AN contains calcium nitrate ? I checked the solubility of CaNO3 and it is almost the same as AN and it is like the same hygroscopic too.

What was the concentration of your H2SO4? Higher concentrations will lead to the decomposition of Erythritol. I would keep my acid at a 90ish % concentration. And pay attention to temperature.

I don't know any reliable way to determine if you have the double salt or not.
What is the source of your nitrate?


Attachment: US1691954A.pdf (98kB)
This file has been downloaded 50 times



[Edited on 31/5/18 by joseph6355]




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[*] posted on 31-5-2018 at 12:04


Usually i am using AN but it looks it contains calcium too. I will have some fresh Kno3 tomorrow and i will try again. My h2so4 is azeotropic (98%)
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[*] posted on 31-5-2018 at 13:12


On amateur field is usually, that the way is a target. Now come times, when will necessary use distillation device. I know, that is difficult way, but ice packs are intentionally contamined. And maybe not only CaNO3.



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[*] posted on 1-6-2018 at 03:50


take your ammonium nitrate, calcium nitrate mix, disolve in clean strong amonia water, filter all the crap out, then enjoy the head ache that it is to dry it with out a vacuum system! = pure AN
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[*] posted on 1-6-2018 at 08:23


Quote: Originally posted by underground  
Usually i am using AN but it looks it contains calcium too. I will have some fresh Kno3 tomorrow and i will try again. My h2so4 is azeotropic (98%)

You should dilute it with water until 90% concentration is achieved.




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[*] posted on 1-6-2018 at 09:15


Would it be possible to throw in some sodium carbonate for a metathesis reaction? Calcium carbonate should drop out as a white precipitate as a definitive test, no? Plus, you can measure the amount of precipitate produced, pegged against the sample mass used, to figure out the concentration.



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[*] posted on 1-6-2018 at 13:19


AN will react too relising ammonia.

Quote: Originally posted by XeonTheMGPony  
take your ammonium nitrate, calcium nitrate mix, disolve in clean strong amonia water, filter all the crap out, then enjoy the head ache that it is to dry it with out a vacuum system! = pure AN


I do not have ammonia water. I will try with kno3 and i will let you know
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[*] posted on 2-6-2018 at 10:47


I did try with some fresh kno3. Reaction was looking better as the Nitric acid started to fume from the first additions of kno3 indicating concentrated mixed acid. Unfortunately i did have 0 yields again :( I really dunno what is going on. I think the problem is the H2SO4 because i did got some ETN from my last old H2SO4. Another thing i am thinking is my old Erythritol, i got it for 4-5 years, but as i said before, i got some ETN. If Erythritol would be the problem i would not get any ETN at first right ?
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[*] posted on 2-6-2018 at 12:44


both need to be very dry and it's important to rise the temperature to about 20°C for 1 hour at the end of the nitration (2 h total), otherwise it tends (the KNO3 route) to produce water soluble trinitrate (and lower nitrates)
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[*] posted on 2-6-2018 at 14:24


All salts are into a desiccator bag with cacl. I was doing the nitration at 35°C

I think that this is not an issue as long as i have seen patents making ETN at 40-60°C

https://www.google.com/url?sa=t&rct=j&q=&esrc=s&...

I will give it a try tho not over 20°C, but i don't think it will change anything.
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[*] posted on 2-6-2018 at 21:47


You can try hold temperature at 4 - 6 C during addition of Erythritol. Mixing 30 minute at 6 C. And after increase tepm. on 20 C on 30 minute. We are everybody only disciples. For attempt I recommend only 2,5 g E.



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[*] posted on 3-6-2018 at 09:29


Laboratory of Liptakov thanks a lot! I tried a small batch (50ml SA/30g Kno3/7,5g E) holding the temp below 10 C during addition of Erythritol. I let it for about 30-40 min after the addition of Erythritol. I did got some ETN at last. Yields dont look that much, maybe 4-5g recrystallized , they are drying right now. Maybe if i would let it 30 min more i would take some more BUT at least i got something. It looks like high temp destroy the E while you adding it into a mixed acid. I guess after 30 min from the last add of E you can increase the temp more cause there is mostly low nitrated E. I believe low nitrated E is not that much sensitive to temperature as pure E is.
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[*] posted on 3-6-2018 at 11:28


~ 30 % yield or 5 g of ETN from 7.5 g of erythritol is about as good yield as ur gonna get (via the KNO3 route). Not bad, since producing 100 g of ETN will take only 1 l of acid, 600 g of KNO3 and 150 g of erythritol and 1-2 l of EtOH + some baking soda, so you're looking at about 35 $/100 g of ETN which isn't bad at all.
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[*] posted on 3-6-2018 at 11:59


A bit expensive, isnt it ?
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[*] posted on 3-6-2018 at 12:13


That's enugh for 70 - 100 blasting caps or 4 hard core PBX charges, not bad for 35 $ (if u live in the US).
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[*] posted on 3-6-2018 at 13:38


It's nice, Underground. As a next step, I propose this attempt. Reagents: E = very fine and very dry 5g. KNO3 very gentle and very dry 20g. SA 95-98% 33ml. Procedure: Cool SA on - 10C. Add E in small parts (5x1g) . Keep the temperature below + 5 ° C. Dissolve all E in acid. Add KNO3 in small portions of 5 x 4g. Keep the temperature below + 5 ° C during addition. Stir for 10 minutes at + 5 ° C. Increase temperature to + 10 ° C (10 minutes) Increase temperature to + 20 ° C (30 min). Following is the usual process, pour into cold water and so on. We are all just disciples: But we can learn from observation. And also from patents. It's just a suggestion. Maybe it will not work......:cool:



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[*] posted on 3-6-2018 at 13:50


I have tryed in the past dissolving E into SA and i got low yields. Other members here in this forum got the same bad yields with this method too. But maybe i will try again, :D
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[*] posted on 3-6-2018 at 13:54


https://en.wikipedia.org/wiki/Erythritol_tetranitrate
............Increase temperature on + 20 C on 60 minute...........
http://citeseerx.ist.psu.edu/viewdoc/download?doi=10.1.1.653...

[Edited on 3-6-2018 by Laboratory of Liptakov]




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[*] posted on 3-6-2018 at 14:30


From what you linked:

"The erythritol/sulfuric acid mixture was added
to the nitric/sulfuric acid mixture over 30 minutes while maintaining the temperature below
10 C. After addition was complete, the mixture was warmed to 35 C and stirred for 1 hour."

And from Wiki

"It is important to perform the last step at about 20°C - for about an hour in the case of KNO3/sulfuric route. Lower final temperature is going to yield only the trinitrate and lower esters and these are soluble in water"


So it looks like it works like this:

1st you add your E at low temp so it wont decomp from the mixed acids. E into mixed acids at low temp produce lower esters. Next, you need to increase the temp in order to fully nitrate the lower esters. Obliously low nitrated esters are not so sensitive as pure E as i said. On your pdf it is said as high as 35 C.



P.S.

From wiki: "Ammonium nitrate is superior in terms of yields and ease of manufacture."

I can see the reason why AN is easier to work with vs kno3 but i really dont see the reason why you could get better yields.

[Edited on 3-6-2018 by underground]
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[*] posted on 3-6-2018 at 14:42


These are all my wiki edits, based on experimentation and experience....
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[*] posted on 3-6-2018 at 15:13


I see. Maybe when i got time i will try few small batches at various temp, increasing the temp on every batch till I got the best yields. Also i was thinking to lower the amount of E cause the yields are always low (40-50%) I am sure much acid is wasted on lower nitrated esters, so reducing the ammount, you could have stronger acids to fully nitrate the E
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[*] posted on 3-6-2018 at 16:22


Quote: Originally posted by underground  

I did not have any issues in the past. My used to yields was about 50-60% which is ok for ETN and i was still satisfied with it,


You already had a problem back then. Your yields should be closer to 90%
That's with 96% H2SO4 and azeotropic HNO3 at least.

I have read here and there on the forum many poor ideas in the synthesis of ETN or others:
Adding Erythritol mixed with a nitrate salt in the cooled sulphuric acid was one that shocked me. Hotspots ! Decompositon of the product ---> Less yield.
Finishing the nitration at 40% and stop where fumes appear ?
Lost N, some product oxydized, NOX ---> Less yield
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