Sciencemadness Discussion Board
Not logged in [Login - Register]
Go To Bottom

Printable Version  
 Pages:  1    3  ..  9
Author: Subject: ETN synthesis problem
The_Davster
A pnictogen
*******




Posts: 2858
Registered: 18-11-2003
Member Is Offline

Mood: No Mood

[*] posted on 25-11-2006 at 15:06
ETN synthesis problem


Whoa... 2 in an hour.

Chemolobotomy seems to be a reincarnation of If_6_was_9, and other guises. I deleted some posts that were in completly wrong threads, but they keep coming. Same crap as usual.

Lassofix is some sort of spambot, post left in detritus currently.

[Edited on 21-12-2017 by Bert]




View user's profile View All Posts By User
vulture
Forum Gatekeeper
********




Posts: 3331
Registered: 25-5-2002
Location: France
Member Is Offline

Mood: No Mood

[*] posted on 25-11-2006 at 15:14


10-4, both have been banned as of now. Thanks for reporting this.



One shouldn't accept or resort to the mutilation of science to appease the mentally impaired.
View user's profile View All Posts By User
Deceitful_Frank
Hazard to Self
**




Posts: 82
Registered: 5-11-2005
Member Is Offline

Mood: Pensive

[*] posted on 13-12-2006 at 11:31
ETN synthesis problem


Hey guys, just a quick question concerning the synthesis of ETN using erythritol, ammonium nitrate and sulphuric acid.

The ratios that I use are 1:4:12 but mass but towards the end of the erythritol addition to the mixed acids, everything becomes so thick that the whole deal is VERY difficult to stir with broken thermometers and partially nitrated shit being the result!

Does anybody know of an "inert" liquid that I could add to the reaction mix to thin it all down, make it easier to stir and promote homogenuity and give me a purer end product?

...sure I could just use more AN and acid but Ime not keen to waste my chemicals unnecessarily and dont want to lose any more ETN to dissolution in the acid bath.

Any help or ideas would be gratefully recieved,

Regards.
View user's profile View All Posts By User
ZoSo357
Harmless
*




Posts: 16
Registered: 30-8-2005
Location: Here
Member Is Offline

Mood: I dropped it :(

[*] posted on 13-12-2006 at 12:16


How cold are you keeping your nitration bath? Many people have had best success around 15 - 20* celcius. A slightly warmer bath should keep it a little less viscous.



View user's profile View All Posts By User This user has MSN Messenger
Deceitful_Frank
Hazard to Self
**




Posts: 82
Registered: 5-11-2005
Member Is Offline

Mood: Pensive

[*] posted on 13-12-2006 at 12:46


Good point! I usually work between 5 and 10C... Deffinately worth a go though I do work indoors without a great deal of ventilation and when my nitration bath has topped 20C, the HNO3 mist can become a little trying!
View user's profile View All Posts By User
hinz
Hazard to Others
***




Posts: 200
Registered: 29-10-2004
Member Is Offline

Mood: No Mood

[*] posted on 13-12-2006 at 15:25


I would simply buy a destillation setup and work with pure nitric/sulfuric mix, a basic destillation setup simplifies so many things, it's really worth it's money.
If not, you might also mix your nitration acid with some methylene chloride, it should be inert against it, as it's used to seperate HNO3 from water, but I don't know anything about the solubility of ETN in CH2Cl2, so maybe CH2Cl2 dissolves some of the product which has to be removed afterwards.
After my attemps to nitrate nitromethane to tetranitromethane (attack of NO2+ on CH2=NOOH <=> CH3NO2, when the aci form deprotonates, CH2 might have a negative charge) I think NM is also stable against HNO3, my mechanism somehow doesn't work. So it might be used to thin your mixture (ofcourse in absence of an aldehyde or ketone;) ). But it will increase the explosion hazard. polar stuff like pentane you can forget because they are inmiscible.

[Edited on 13-12-2006 by hinz]
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 13-12-2006 at 18:58


Bringing the temp to 15-20 C is a great place to start. The common issue encountered as you describe is that if nitration is successful (re: yield) you should have a thick mass - thus your nitration is successful. The most important issue is to make sure to elimininate hot spots via stirring of course. If you are using a magnetic stir-bar, often the size is too small to be of much use when the solution is thickened. A significanly thicker stir-bar would take care of that as well. However some of the methods used to deal with the issue has been to use HNO3 at 70% as an additional element to make stirring successful. If that (HNO3) is not available and additional equipment is also not available, a longer time frame in one's additions MAY make the solution mixable as temp maintains itself at 20 C. But to address the question directly; there is no reason why one has to attempt the highest yield per ratio. Meaning that you could simply use more nitration acids in ratio to eurythritol.

Here is some stuff...hope it helps

[Edited on 14-12-2006 by quicksilver]

Attachment: ETN_notes-2006.pdf (48kB)
This file has been downloaded 8195 times





View user's profile View All Posts By User
ZoSo357
Harmless
*




Posts: 16
Registered: 30-8-2005
Location: Here
Member Is Offline

Mood: I dropped it :(

[*] posted on 14-12-2006 at 14:15


Hinz, Something that (may be unsual) yet tends to be a problem with HNO3 and H2SO4 is that many people have trouble getting a good nitration for ETN. Their yields tend to turn out worse than with a nitration using a nitrate salt and H2SO4. From what I've read about people on APC forum, and my experiences, the best way to get ETN to nitrate and give you the best yield during your precipitation is to use KNO3 and H2SO4.

Yeah, the KNO3 will be a little thicker and harder to stir than NH4NO3, but the end product has been more efficient in precipitating out larger amounts than with NH4NO3 or HNO3.

I'm not sure of the exact reason why, since this tends to be the opposite with things like nitrocellulose and other nitrateable compounds(nitrating more efficiently with ammonium nitrate as a salt, or with pure HNO3), but there's a discussion of ETN synthesis on the *old* APC forum pertaining to the issues people had with nitrating erythritol.

Goodluck deceitful frank.

[Edited on 14-12-2006 by ZoSo357]
View user's profile View All Posts By User This user has MSN Messenger
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 14-12-2006 at 17:16


You know you bring up an interesting point; the nitrate salt. A few people have done some testing w/ different nitrates but the one thing that many folks don't do is reduce the particulate size to start out with. From what little experimenting I have seen, if the particulate is sub-sieze in size to begin with a heck of a lot of problems are reduced (pun intended). Another thing that stands out as a variable w/ many experiments in nitration w/ solid nitrates is that either the H2SO4 or the nitrate may have impurities to begin with. However alk metal nitrates often have advantages in some nitrations. I know that a search in the forum here would turn up some info on that very subject. The question I have often wondered is IF there is an optimum solid nitrate for specific nitratied materials. And there does appear to be some substantiations for using differing solid nitrates.
IIRC some of the best yields with ETN have been HN4NO3 nitrations re-crystalized with methanol. Often what is delivered prior to re-crystalization can be outstanding. That is not to say that Na or KNO3 would do better; one would need to simply work with a given gram size of starting material and actually weigh it when totally dry. Occationally those yields are diminished during re-crystalization. Acetone appears to be just TOO an effective solvent for ETN with the end result being crystals that are irrregular platlettes which are much less dense than w/ the use of an alcohol as solvent. The lack of density makes for poor preformance as an energetic material when compaired to a dense granular crystal.
I have a lot of info on ETN and if I can dig it up I'll post it to this thread (if it keeps on going). Most all the stuff I had thought was ever done was hobbiest stuff during the last few years BUT....there was some stuff DuPont did during the patent application period. And interestingly enough a lot of it had to do w/ re-crystalization ....

[Edited on 15-12-2006 by quicksilver]




View user's profile View All Posts By User
Deceitful_Frank
Hazard to Self
**




Posts: 82
Registered: 5-11-2005
Member Is Offline

Mood: Pensive

[*] posted on 15-12-2006 at 14:15


Of course, distilling pure WFNA and using this to nitrate my erythritol and then precipitating with sulphuric acid is the most efficient route to highly nitrated ETN of good stability and in great yeild but at present, in the absence of the glass, the space and the means, the acid/nitrate method cannot be ignored for its simplicity. Crude and tedious albeit, ime sure that if all minor creases can be ironed out, we could have a good honest no-fuss route to ETN.

For now I think I will scrap the idea of trying to water down the nitration as like quicksilver stated, the very fact that my nitration thickens up stiff proves the production of highly nitrated erythritol thats insoluble in my nitration bath! I suppose it depends where my priorities lie... do I want to get the maximum ETN per erythritol or do I want to conserve my somewhat limited quantity of acid and ammonium nitrate. Hell maybe I just want maximum nitric ester per cash spent on reagents!

Fortunately I have nearly a kilo of erythritol so never likely to run out any time soon. I use cheap-ass drain cleaner of 95-97% purity and full of red dyes and shit. Although it severely gunges up my EGDN and lowers yeilds, it doesnt seem to contaminate or get in the way with ETN synths... plus its OTC and after a recent close call with the law, Ime keen to save my hard-won clear 98% reagent grade acid for the experiments that REALLY need it!

This leaves the question of ammonium nitrate. It would appear to be my most difficult to acquire reagent for this synthesis as I have no OTC supply and internet sales of the compound are watched by the government. Ive managed to "find" 7Kg but with so many uses it seems apparent that it would be wise to design a synthesis for ETN that gives the highest yeild of nitric ester per gram of ammonium nitrate used.

So taking my original numbers of 1, 4 and 12 by mass which gives approximately a 50% excess of nitric acid than is need to fully nitrate the erythritol plus a mole of sulphuric acid to mop up every mole of water produced by the esterification... and a little extra to thin the whole deal down a bit. Could I maybe reduce the ammonium nitrate to 3 times the mass of the erythritol and get a good yeild with just a 15% excess of nitric acid or is this going too far?

Maybe I should stick with those original ratios and to thin it all down, just increase the quantity of my cheapest and easiest to acquire reagent, the sulphric acid?

Either way, I have found what appears to be the perfect way to recrystalize raw ETN (with a view to remove lower nitrates, acidity and give larger, easier to handle crystals)

I use generic methylated spirit from the hardware store. Mainly ethanol with methanol, pink dye, bitrex and a small amount of gasoline added. I think the gas is there to prevent it mixing with water and to make it nigh on impossible to distill out the ethanol for consumption. Therefore it isnt taxed and is very cheap to buy.

Basicly all I do is add the dried, raw and neutralised ETN to a small amount of meths in a sealed glass bottle (trial and error needed) and heat to 55C to dissolve (dont let it go over 60C or the ETN will melt or precipitate as a liquid... then its FUCKED!)

When its all in solution and around 55C I take the glass bottle and place in a LARGE jar or hot water at around 57-58C and leave the whole lot to cool very SLOWLY. the ETN precipitates nice and slow into large crystals of much higher bulk density than when in the raw newly nitrated state. And so into the freezer to get the last ETN out of solution and hopefully leaving the more soluble lower nitrates behind dissolved in the meths :D


[Edited on 15-12-2006 by Deceitful_Frank]

[Edited on 15-12-2006 by Deceitful_Frank]
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 16-12-2006 at 06:27


Re-crystalization is a key issue with PETN, ETN, MHN, etc - The reason I mention the fact that methanol will work in that capasity (w/ ETN) is that it is available OTC via auto supply stores..... The more one maintains simplicity in experiments the better chance one has for "all the creases being ironed out"....Thus there will be no complications with bizarre and extrainious stuff left in your ETN at the end of the synth.....when you get really pure ETN in course, heavy, well formed crystals; it is some very interesting material, indeed.



View user's profile View All Posts By User
Sickman
Hazard to Self
**




Posts: 98
Registered: 9-5-2004
Member Is Offline

Mood: Icy and I see!

[*] posted on 16-12-2006 at 23:26


This is a good topic!

I've been hearing people complain for years about thick nitration mixtures and broken thermometers and so on.

I really don't know what the ultimate answer is. On the one hand if you add an inert solvent you are diluting your acids, which may result in poor nitration, low yield and the need for longer nitration periods. On the other hand concentrated nitric acid may be the answer, but it is not always the best choice in a given nitration such as for erythritol, because of lower yields, problems with oxidation of the erythritol and higher costs for the acid.

Thus far what has worked best for me is to ditch the glass thermometers for a good plastic cooking spoon. They don't break and the plastics I have used have been completly inert to the reaction. In combination with the plastic spoon a much longer nitration period could'nt hurt much in the case of ETN.

Because the ETN nitration using alkali metal nitrates and even AN is very thick like icing, a plastic spatula may prove to get the mixture mixed the best if a mechanical help is not available.;)

If you are a wealthy fellow, unlike some of us, the answer is obvious. Use a greater acid/nitrate to erythritol ratio, but who among us is a wealthy fellow?:D

On a similar note: has anyone noticed a difference in final yield when the acid and nitrate is first mixed and then the erythritol is added to it, as opposed to adding the erythritol to the sulfuric acid and then adding the nitrate to that. Upon studying Urbanski a bit I see that order of addition does matter in many cases. Urbanski noted that adding the substance to be nitrated to a mix of acids can result in higher nitration than first sulphonating the material and then adding the nitrating agent to that, (unfortunatly this can also lead to oxidation of the material to be nitrated causing lower yield IMHO). The reason is he explains is that the material being nitrated will have far more contact with the nitration agent in a much higher concentration, as opposed to a more isolated environment were only a small amount of nitratable material is in contact with the nitration agent.

However, first sulphonating the material to be nitrated, for example phenol, in the case of picric acid, has many benifits including easier nitration and less oxidation.

I wonder if there can be a happy balance. I think I might try simply mixing a pre-calculated amount of powdered erythritol with powdered AN and then add the powdered mix directly in portions to the sulfuric acid. Who knows a little tinkering around with ratios and orders of addition may lead us too the highest nitration levels, lowest oxidation of erythritol from the nitric acid and highest yields.
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 17-12-2006 at 10:38


"On a similar note: has anyone noticed a difference in final yield when the acid and nitrate is first mixed and then the erythritol is added to it, as opposed to adding the erythritol to the sulfuric acid and then adding the nitrate to that. Upon studying Urbanski a bit I see that order of addition does matter in many cases. Urbanski noted that adding the substance to be nitrated to a mix of acids can result in higher nitration than first sulphonating the material and then adding the nitrating agent to that, (unfortunatly this can also lead to oxidation of the material to be nitrated causing lower yield IMHO). The reason is he explains is that the material being nitrated will have far more contact with the nitration agent in a much higher concentration, as opposed to a more isolated environment were only a small amount of nitratable material is in contact with the nitration agent."


This is a very important issue. Does this issue have more relevence to a phenol than a solid alcohol? It would seem to be a damn good experiment for a solid alcohol. From what I have read not all nitric esters react the same during nitration. This concept (addition to HNSO4) would not make a significant difference with glycerin I believe but with mannitol or sorbitol it is manditory for good results. Erythritol nitrates very easily; that is shown by the speed of crystaline build-up during the addition phase. However, if one has taken care to be thorugh when creating a nitration acid mix (making sure that the solid nitrate it totally dissolved in the HNSO4, covering the beaker with Al foil to prevent fumes, high oxcidation rate, etc & achieving a clear solution) and one's additions are at a CONSISTENT level, the build-up of heavy crystals should only occur at the end of the nitration. Best yields and best control oveer the nitration are achieved if the nitrating acid is clear, cold and the additions are consistent in time margin and weight.. ... Where there has been issues often can be traced back to inconsistency to temp and addition time/weight ratio. There is a great book (if you can ever find a coy BUY IT!) intitaled "MILITARY EXPLOSIVES" by Weaver, published by Wiley in 1906. I have seen a copy from 1917 (4th edition) wherein the actual nitation machines used by DuPont are illustrated and discussed at length. They didn't leave the ratio weight/time addition to chance as it became critical to yield, safety, and control of quality. Where I am going with this is that IF that nitration acid is COLD, just out of the 'fridge and the additions are consistent, the acid should warm during the peak of crystal production and lower it's viscosity enough due to warmth (20C) to be mixable without great difficulty as the yield has peaked. With ETN, once the yield has peaked the material should sit for a period of time in cold (no hot spots) and the bearing of a 70% or greater yield should maintain itself on the correlation of those above illustrated issues.




View user's profile View All Posts By User
Sickman
Hazard to Self
**




Posts: 98
Registered: 9-5-2004
Member Is Offline

Mood: Icy and I see!

[*] posted on 18-12-2006 at 01:16


Quicksilver,

The book you mentioned can be read online at:
Notes On Military Explosives by Erasmus Weaver

You can also download a free PDF file of the book at:
Notes On Military Explosives by Erasmus Weaver PDF

70% yield is not that great in my book. In my mind the possible culprits inhibiting a higher yield may be:

1. Oxidation of the erythritol by the nitric acid due to the acid being too concentrated or nitration temperature being too high may also cause oxidation to occur.

2. Incomplete nitration due to lack of sufficiant nitrating agent and a need for longer nitration periods. The loss of fixed nitrogen in the form of nitrogen oxides (brown gas), often due to excessive heating of the nitration bath also falls into this category of loss.

3. Problems with solubility, including incomplete crystallization of ETN from the nitration bath. This problem may be solved by salting out of the ETN by adding an additional amount of ammonium sulphate or any other salt, preferably a sulphate, that would be more soluble in the nitration bath than the ETN is, after the nitration process has been completely resolved.

4. Careless filtration and recrystallization methods.

I find it unlucky that nitric esters have so many stability problems, with PETN, and perhaps ETN also, being the most stable of the bunch.

As far as order of additions in manufacture of various explosives goes, the optimum order of addition will depend on how susceptible the material to be nitrated is to oxidation and the fact that first sulphonating the material often makes it easier to introduce the nitrogen groups by way of reduction of the sulphonated groups. The nitration of phenol is a good example of this trait.

I've learned that each nitration is unique; each has it's own necessities to be met for best performance and safety.
View user's profile View All Posts By User
a_bab
National Hazard
****




Posts: 449
Registered: 15-9-2002
Member Is Offline

Mood: Angry !!!!!111111...2?!

[*] posted on 18-12-2006 at 04:08


Sickman, the link doesn't work anymore. Can you uplod the book somewhere else please?
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 18-12-2006 at 10:20


Here is some more info patents, pics; it picked up where the other PDF file left off...


** That link for Weaver worked for me just fine...(?)



[Edited on 19-12-2006 by quicksilver]

Attachment: ETN-pics-Lab-pat.pdf (562kB)
This file has been downloaded 7700 times





View user's profile View All Posts By User
maxidastier
Hazard to Others
***




Posts: 118
Registered: 3-4-2010
Member Is Offline

Mood: No Mood

[*] posted on 3-4-2010 at 08:26


hello,

I'm just having one only question: Can I use Soda instead of Baking Soda?
View user's profile View All Posts By User
hissingnoise
International Hazard
*****




Posts: 3727
Registered: 26-12-2002
Member Is Offline

Mood: Pulverulescent!

[*] posted on 3-4-2010 at 09:04


The only thing I have against washing soda is its basicity. . .
Doesn't every home have some baking soda lying around?
View user's profile View All Posts By User
maxidastier
Hazard to Others
***




Posts: 118
Registered: 3-4-2010
Member Is Offline

Mood: No Mood

[*] posted on 3-4-2010 at 09:15


But do you think those 50 g packages are enough?
View user's profile View All Posts By User
hissingnoise
International Hazard
*****




Posts: 3727
Registered: 26-12-2002
Member Is Offline

Mood: Pulverulescent!

[*] posted on 3-4-2010 at 09:34


How many tons of nitrated material do you intend producing?

But seriously, amounts of bicarbonate needed for neutralisation are very small if you've washed your product with water first.
5% solutions are fine!



[Edited on 3-4-2010 by hissingnoise]
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 3-4-2010 at 10:20


If you re-crystallize with commercial ethanol (Everclear, etc) you will have a 95% - 5% H20 solvent. The small percentile of water will maintain the anti-acid product so as to make that available to the crystal. There is ETN, MHN, etc hanging around for years - as bright and pretty as the day it was made.
View user's profile View All Posts By User
maxidastier
Hazard to Others
***




Posts: 118
Registered: 3-4-2010
Member Is Offline

Mood: No Mood

[*] posted on 3-4-2010 at 12:02


Really? Why do so many get high yields with the commerical Ethanol?
I have distilled my own METHANOL, so I get only around 90%.
Do you really think that's waste now? I have some 50 g ETN to recrystallize, please don't tell me it won't work....:(

[Edited on 3-4-2010 by maxidastier]
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 4-4-2010 at 09:13


Methanol is fine - no problems. The issue is that commercial ethanol has a small % of water and anti-acids (such as bicarbonate of soda) is very soluble in water. Thus when you re-crystallize, you have direct application of the anti-acid with the crystal. This is not to say that less soluble material (solvents) to anti-acidic products won't neutralize your material. However the level of neutralizer is available with a fraction of water within the solvent.

IF however your methanol has a fraction of water - you should notice that your bi-carbonate should dissolve within better than anhydrous solvent materials. The idea is to completely wash until neutral, re-crystallize with an anti-acid (& best, w/ a stabilizer) thus maintaining a synthesis that won't give way to existing acids lurking about.

Some materials require a continued wash is a desired shelf life of many years is anticipated. Most notably NG. I believe that some of the oldest nitric ester in existence is NG but it required a wash periodically through decades. properly synthesized, the majority of nitrated polyols will last quite a long time if kept from acid, UV, heat (>40 C), etc.

[Edited on 4-4-2010 by quicksilver]
View user's profile View All Posts By User
grndpndr
International Hazard
*****




Posts: 508
Registered: 9-7-2006
Member Is Offline

Mood: No Mood

[*] posted on 4-4-2010 at 19:41


Automotive 'Heet' , (yellow bottle methanol AIRC)MSDS lists content as 99% methanol,.02 xylenes,0-,m-,p- isomers)
Unknown % corrosion inhibitors.Might need add little dist water to incorporate the bicarb.:)Urea a reasonable stabilizer?If that could be incorporated at some point particularly during a recrystaliztion the urea etc, should be incorporated consistently
thruought?

[Edited on 5-4-2010 by grndpndr]
View user's profile View All Posts By User
quicksilver
International Hazard
*****




Posts: 1820
Registered: 7-9-2005
Location: Inches from the keyboard....
Member Is Offline

Mood: ~-=SWINGS=-~

[*] posted on 5-4-2010 at 08:08


Urea, Betain, Diphenyamine all work fine as a stabilizer. The prime factor is getting it into the material instead of superficially covering it.
Most of the time, if the synthesis has acid lurking about - it will be noticed. However, there ARE materials or conditions that do a good job of disguising the impurity.
Most nitric esters become a problem when they decompose. At the turn of the 20th century, paper with various indicators were often included in packages of commercial energetic materials. Any white paper in contact will change color if the acidic impurity is high enough. Occasionally they had been constructed so that it would not be immediately apparent that they were there as a "problem indicator" (printed advertisements, etc) so as not to frighten the buyer. However the large commercial powder salesman would know and dump his samples (or whole order) if they showed a problem. In the heat, poorly made products had problems surface quickly & the results could be calamitous.

A pretty interesting book printed by the ISEE is entitled "Explosives -100 years Ago, More of Less", Hopler. It has some unique stories and advertisements in it. That was the same time in history that many of the synthesis that are talked about here were the popular level of science!
View user's profile View All Posts By User
 Pages:  1    3  ..  9

  Go To Top