Sciencemadness Discussion Board

Trinitrotoluene preparation

 Pages:  1    3

Rosco Bodine - 27-11-2014 at 00:20

Here is one example US4084995

Attachment: US4084995 Preparation of a cap sensitive particulate explosive composition comprising calcium nitrate.pdf (1.2MB)
This file has been downloaded 708 times


Hennig Brand - 27-11-2014 at 13:23

Thanks for the patent.

I just wanted to add that the DNT produced still had a slight smell of mononitrotoluene. If this was seen as a problem there are several things that could be done to push the nitration more into the DNT-TNT region and farther out of the MNT-DNT region. The 10% excess nitration mixture specified could be increased to 20% or more. The temperature could be increased from 80C to 90C for the 2 hours at the end of the nitration. The 2 hour end of nitration high temperature "nitration finisher" could also be run for more than 2 hours. There are probably other ways to push the nitration farther as well. 
 

[Edited on 28-11-2014 by Hennig Brand]

Rosco Bodine - 27-11-2014 at 20:26

Here is an interesting patent US2435314 attached

Another interesting patent is GB501034 attached


Attachment: US2435314 TNT Nitration method.pdf (462kB)
This file has been downloaded 580 times

Attachment: GB501034 nitration catalysts.pdf (212kB)
This file has been downloaded 493 times

[Edited on 28-11-2014 by Rosco Bodine]

Hennig Brand - 27-11-2014 at 23:17

I am quite sure that I have successfully produced TNT using sodium nitrate and 98% sulfuric acid. I have a bunch more pictures to share, but I am having a little trouble logging onto the forum except using the 4G network and my phone. SO3 was used to soak up water in order to produce the 98% H2SO4 from less concentrated acid. The sodium nitrate was made from sodium bicarbonate and ammonium nitrate; a slight excess of ammonium nitrate was used and the two reactants were boiled in water until the smell of ammonia was extremely faint. More or less the same setup as was used to produce the DNT was used, but I ran into a little trouble with the process. I first made >99% H2SO4 and then I could only get ca. 1/4 to 1/3 of the sodium nitrate to dissolve in it. In a moment of unclear thinking I added an amount of water necessary to bring the acid down 1% to >98% which only seemed to increases the solubility a little. In retrospect 98% sulfuric acid is probably about right anyway, but adding water was not the way to achieve it. In twenty minutes or so I came up with "the plan"; the solid sodium nitrate would be dissolved by putting the nitration mixture into the flask and bringing it up to the reaction starting temperature (80C). The DNT was kept in a small beaker on a small warming tray and kept in the molten state enough above its solidification point that it would not plug the glass eye dropper/pipette used to add it to the reaction flask. The solid nitrate did dissolve at the elevated temperature and other than a few minor issues with DNT solidifying in the pipette everything went smoothly. I will explain in more detail with pictures and quantities used, etc, when I can log on from a full sized computer.


[Edited on 28-11-2014 by Hennig Brand]

TNT Production From DNT, Oven Dried NaNO3 and 98% H2SO4

Hennig Brand - 28-11-2014 at 07:17

I was using the article Rosco posted earlier, from "The Journal of Industrial and Engineering Chemistry", which had in it the tabulated results of a series of TNT synthesis experiments. I used experiment No. 16 as a rough guide. The article was based on MNT to TNT, but I still used the same mass fractions even though I was going from DNT.

Ammonium nitrate was used to nitrate the toluene to DNT, however, there are a lot of indications that sodium nitrate will not decompose the way ammonium nitrate does at higher temperatures. Ammonium nitrate decomposition products could cause damage to the intermediates or possibly the products of the reaction and will lower the strength of the nitration mixture at the very least. It was decided that sodium nitrate would be used for the last stage of nitration.

From DNT to TNT
Nitration Mixture Composition:
82% Sulfuric Acid
16% Nitric Acid
2% Water

(75% Excess Nitric Acid)

For 1g of DNT:

1g / (182.134g/mol) * 1.75 = 0.00961 moles of HNO3 Specified

HNO3 Production:
mass of NaNO3 needed = 0.00961 * (84.9947g/mol) = 0.8168g
mass of H2SO4 needed = 0.00961 * (98.079g/mol) = 0.9425g
produces 0.00961 moles * (63.01g/mol) = 0.6055g HNO3

Reaction Mixture H2SO4:
mass of H2SO4 needed for nitration mixture= 0.6055g/16 * 82 = 3.103g
mass of H2O specified for nitration mixture = 0.6055g/16 * 2 = 0.07569g

Per 1g of DNT use:
0.6055g HNO3
3.103g + 0.9425g = 4.0455g H2SO4 (anhydrous)
0.07569g H2O

Started off with H2SO4 of >95wt%. From previous experience it was known that 130g of NaHSO4 containing pH down would produce about 25g of SO3 and 1.2g of water by the method used. Since about 260-280g of NaHSO4 was used it was assumed that about 50g of SO3 and 2.4g of water would be produced.

10.67g SO3 to tie up assumed 2.4g water in SO3/Oleum produced
39.33g SO3 left from assumed total of 50g
39.33g SO3 / (80g/mol) * (18g/mol) = 8.85g of H2O it can convert to H2SO4

Assume starting with 95% H2SO4 and are aiming for 99%. There is enough SO3 (39.33g) to convert 8.85g of H2O to anhydrous H2SO4. The next time I would do it right and add enough H2SO4 to get to 98% acid and not add any water after the fact.

99% - 95% = 4% water needs to be removed

H2SO4 needed = 8.85g / 0.04 = 221.23g of 95% H2SO4 (I added 226g by mistake, but the acid still titrated at over 99% after the acid was added to the SO3)

95% H2SO4 added: 221.23g
SO3 plus H2O it binds with from SO3/Oleum produced: 13.07g
SO3 left from assumed 50g total: 39.33g
Total Produced = 273.63g of 99% H2SO4

Can Nitrate: 0.99 * 273.63g / 4.0455g = 67.0g of DNT
NaNO3 needed = 67.0 * (0.8168 g NaNO3/1g DNT) = 54.7g

Note:
Then I did something foolish and added 2.7g of H2O to bring the water concentration in the nitration mixture from about 1% to about 2%. This is not a bad thing in a way, as this amount of water can actually be advantageous for the reaction, but a lot more 98% sulfuric acid could have been produced by adding more 95% H2SO4 instead of water. This would have allowed me to nitrate much more DNT (84.2g instead of only 67.0g).

Procedure:
As stated above the oven dried sodium nitrate was added to the sulfuric acid and then put in the 1L reaction flask. The temperature was brought up to about 80C to start the reaction and then the pre-warmed and molten DNT was pipetted in to the reaction flask about 1mL at a time over the course of 2 hours. During the addition time the temperature was kept between 80 and 90C. After the addition was complete the temperature was slowly raised. By the end of the second hour the temperature was up to 130C and was kept in the 130-135C region for another 2 hours. I think I will use a lower maximum temperature next time (120-125C) since on reviewing the article previously mentioned looks as though this range generally gives the highest yield of the purest product.


SO3 Production Pictures:

Driving Off Water.jpg - 495kB SO3 Collection.jpg - 480kB SO3 Production Near End.jpg - 513kB Dissolving SO3 In Concentrated H2SO4.jpg - 354kB


Preparing Reactants: (adding the first bit of NaNO3 to the >99% H2SO4 caused it to fume profusely)

DNT and 99 percent H2SO4.jpg - 456kB Sodium Nitrate Added to 99 Percent H2SO4.jpg - 448kB


[Edited on 29-11-2014 by Hennig Brand]

Reaction Progression Pictures

Hennig Brand - 28-11-2014 at 07:35



DNT In Beaker And Sodium Nitrate-H2SO4 In Flask.jpg - 195kB DNT Addition Between 80 and 90C.jpg - 255kB Raising Temperature After Last DNT Addition.jpg - 261kB Beginning Of Hour 1.jpg - 263kB End of Hour 1.jpg - 231kB End of Hour 2.jpg - 244kB End of Hour 3.jpg - 255kB End of Hour 4.jpg - 240kB TNT Floating On Acid.jpg - 179kB TNT Solidifying On Acid.jpg - 181kB


[Edited on 28-11-2014 by Hennig Brand]

TNT Synthesis Post Reaction Work-Up

Hennig Brand - 28-11-2014 at 08:36

In total there were 2 hours of DNT addition and 4 hours of heating at elevated temperature to complete the reaction. The crude TNT was collected in two batches. The first batch, which is reported to be of much higher purity generally (COPAE, etc) is what floated and settled on the top of the mixed acid. The less pure crude TNT was precipitated from the spend nitration mixture by dilution. Since sodium nitrate was used a lot of sodium (bi)sulfate precipitated as well once the acid cooled. The mixture of crude TNT and sulfate was filtered out and well rinsed with clean water and then put into boiling water whereby the sodium (bi)sulfate dissolved and the crude TNT became molten and pooled on the bottom. The crude TNT was agitated with magnetic stirring for 15-20 minutes while molten to remove water soluble impurities. Some of the first crop of crystals (cake) collected from the surface of the nitration spent acid was recrystallized from methanol, which formed very well defined crystals and brought the melting point up from the low 70C range to around 80C. The last picture shows the very pale yellow, well formed crystals, of purified TNT.


Yield of washed and dried crude TNT was 44.6g from the first crop and 29.0g from the second crop, for a total yield of crude TNT of 73.6g.

Theoretical Yield = 67g / (182.134g/mol) * (227.13g/mol) = 83.55g

%Yield = 73.6g / 83.55g * 100% = 88.1%

Crude TNT Collecting on Acid Surface.jpg - 187kB TNT Crystals Forming and Rising.jpg - 170kB Post Reaction Dilution With Ice and Water.jpg - 173kB


Crude product from first crop washed to remove water soluble impurities.

Melting and Agitating Crude TNT Under Water 1.jpg - 216kB Melting and Agitating Crude TNT Under Water 3.jpg - 201kB Melting and Agitating Crude TNT Under Water 4.jpg - 199kB


Crude product from spent acid processing.

Crude TNT Recovered from Spent Nitration Mixture.jpg - 283kB Melting and Agitating Crude TNT Under Water 2.jpg - 213kB


First Picture: First crop on left & Second crop on right
Second Picture: Sample of first crop recrystallized from methanol with m.p. around 80C.

Crude TNT Products.jpg - 213kB TNT Melting Point Greater Than 80C After Recrystallization From Methanol.jpg - 248kB


[Edited on 29-11-2014 by Hennig Brand]

Rosco Bodine - 28-11-2014 at 08:37

Here are some more patents of interest attached
These are not directly on topic but related to sensitization schemes involving nitroaromatics including TNT and its lower nitrated precursors and analogous nitroaromatics used to sensitize NH4NO3. Small amounts of NH4ClO4 and metal salts of copper, manganese, iron, chromium, or lead can also sensitize NH4NO3 used for OB mixtures. Ca(NO3)2 and nitroparaffins are also sensitizers. Some of these more sensitive systems are sensitive even to a weakest strength available #1 blasting cap, and are probably sensitive enough for use as reactive target compositions, stump ejection convincer applications, beaver dam removers, instant hole in the ground installers, budget soft target demolition tasks, ect.

US4746380 and GB497145 and US3184351

Attachment: US4746380 glycine adduct with ammonium nitrate.pdf (572kB)
This file has been downloaded 566 times

Attachment: GB497145 Glycine Detonation Catalyst Nitronaphthalene.pdf (392kB)
This file has been downloaded 634 times

Attachment: US3184351_Trichlorethylene sensitized NH4NO3.pdf (307kB)
This file has been downloaded 514 times


2.0g of TNT Initiated; 7.6mm id Al, 0.25g DDNP & 0.35g of LA (Unreinforced Configuration & ca. 6000psi Loading Pressure)

Hennig Brand - 28-11-2014 at 09:29

I initiated 2g of the purified TNT shown in the last picture of the last post. I used DDNP in spite of the fact that the only amount left that I had previously made was sitting on a filter paper on a bureau with dust bunnies in it, etc. It only weighed 0.25g even with all the months of accumulated dust. I decided to use it anyway and mixed it with 0.25g of lead azide and pressed that on top of the TNT. Another 0.10g of lead azide was pressed on top as well for a total of 0.35g of lead azide. A tiny bit of basic lead picrate was also used as a flash igniter. There was a detonation with a fairly large cloud of black smoke, but it wasn't very loud and the damage indicated low order detonation. A dent was made in one side of the witness plate and a nice scab was blown off the back however. It reminded me exactly of how picric acid acts when not overdriven hard enough. I have a bunch of sodium picramate stored, so I may make some DDNP soon and perform a decent test.



0.25g of Dirty DDNP.jpg - 199kB 0.25g of Lead Azide.jpg - 164kB 0.5g of 50-50 mix of DDNP and Lead Azide.jpg - 177kB Witness Plate and Cap.jpg - 150kB Set-up.jpg - 460kB Post Detonation.jpg - 277kB


The dent and scab on the right, in the witness plate shots, are from this test.

Top View of Witness Plate.jpg - 176kB Bottom view of Witness Plate.jpg - 166kB


[Edited on 29-11-2014 by Hennig Brand]

Rosco Bodine - 28-11-2014 at 09:48

You would likely get an easier initiation of TNT using an intermediate coupling charge of something more sensitive like styphnic acid, like a half gram increment substituted for a half gram of the TNT as a coupling charge and booster. The same would apply when picric acid is difficult to initiate ....using an increment of styphnic acid would have about the same effect as using half again as much initiator. The styphnic acid is distinctly easier to initiate than even picric acid, maybe requiring about 30% less initiator, and has about the same power as TNT.

Hennig Brand - 28-11-2014 at 11:21

Sounds like a decent solution. The TNT did seem like it just needed a little more kick to get it into high gear. Even if it took as much as 0.6 or 0.7g of DDNP and 0.05 or 0.1g of lead azide to initiate TNT, it would still make reasonably sized caps. I did some research early this morning regarding critical diameters of powdered TNT. I re-found a document I had found half a year ago or so; "Critical Parameters For Detonation Propagation And Initiation of Solid Explosives". It is even more useful now, because of all the data in it regarding TNT. Here are a couple useful graphs which should help one design around any critical diameter issues. I have attached the whole document as well. The brief write-up before the second graph said that the researcher used consistent particle size and 1g/cc loading density for all tests for the graph on the right below.

Detonation Failure Limit Curves for TNT.jpg - 33kB Critical Diameter of Powdered TNT as a function of Initial Temperature.jpg - 49kB


Attachment: Critical Parameters For Detonation Propagation And Initiation of Solid Explosives (2).pdf (4.1MB)
This file has been downloaded 1270 times


[Edited on 29-11-2014 by Hennig Brand]

Hennig Brand - 30-11-2014 at 07:04

Here is a graph with associated equations for TNT & DNT solubility in methanol. Several of the data point values came from the text "Military Explosives" and a few came from other texts and journal articles. The solubility curves maybe shouldn't be crossing at the bottom, but the graph should be reasonable accurate at any rate. Attached is also a table taken from "Military Explosives", showing the approximate concentrations of impurities before and after purification. It is obvious that crude TNT recrystallization from alcohol, or sulfite washes, are not effective for separating DNTs from 2,4,6 TNT, but they are very effective methods for removing the other isomers of TNT. According to COPAE recrystallization from concentrated sulfuric acid is the most effective method, of the purification methods commonly used at the time, to remove DNT. However, the best solution is to run a good strong nitration and convert as much of the DNT to TNT as possible.


TNT & DNT Solubility In Methanol.jpg - 55kB Impurities Present in TNT - Before and After Purification.jpg - 82kB


[Edited on 1-12-2014 by Hennig Brand]

Hennig Brand - 8-12-2014 at 12:44

It looks as though the TNT purification method involving sulfuric acid from COPAE is a washing process and not a recrystallization. Apparently sulfuric acid washes were done as were/are sulfite washes. The crystals of crude TNT are agitated, as a slurry, for an extended period of time whereby chemical reactions take place with the impurities forming compounds which are much more water soluble and easily removed.

A couple updates

Hennig Brand - 13-1-2015 at 12:19

I didn't post this earlier because I have already posted so much in this thread in the last while.

A few weeks ago I ran another TNT synthesis. A few points of interest:

1. Maximum nitration temperature of 120-125C was used instead of 130-135C and the results were at least visually superior. Even the TNT which was precipitated from the spent nitration mixture was a nice pale yellow, not orange like the first synthesis where the temperature was taken all the way up to 135C. I suppose there could be other variables involved as well.

2. For production of DNT from toluene, when I stated earlier that the temperature should be gradually raised from 30C to 80-90C during the course of nitration mixture addition, that was an oversimplification. Especially during the first and even second nitro group addition care must be taken to prevent oxidation. Additions must be slow and even and temperature should not be allowed to climb too quickly or nitrogen dioxide will be produced in unacceptable amounts and oxidation will take place.

3. The best way to push the DNT from toluene nitration farther is to add more nitration mixture (increase from 10% excess to 20% excess perhaps). Increasing the final temperature from 80C to 90C did not appear to produce any better results at least when held for 2 hours as I did in both cases.

I got a better yield when producing SO3 the last time and made enough 98% H2SO4, from 95% H2SO4, to nitrate about 110g of DNT. Shown below is 76g of TNT from that batch, recrystallized from methanol, with melting point around 80C. There was much more product, but it was precipitated at a lower temperature, and some by dilution of the methanol with water, and was not in a dense well formed crystal structure as the sample shown was.


TNT 76g.jpg - 203kB


[Edited on 14-1-2015 by Hennig Brand]

Trotsky - 18-1-2015 at 05:20

I have made some MNT using ammonium nitrate and toluene, following basically the same procedure I used for nc, though with important alterations, such as allowing the temp to remain much higher. I was worried about runaway in doing so, but either a runaway nitration of toluene is difficult or I was lucky.

I washed and rinsed with bicarb, and added it to a stronger nitration bath and allowed it to sit overnight. I plan on bringing the temp to 90C for 2hr and then cooling. Will this be sufficient to arrive at a reasonable yield of DNT?

My intent is to leave it there until I obtain WFNA or using it to sensitize ANFO enough that tannerite will be able to detonate it.

Hennig Brand - 18-1-2015 at 09:34

If you could post the quantities and reaction conditions used it would be much easier to help you. I will offer the following though, the nitration of toluene to MNT, or even DNT, does not require the strongest acids and if run properly is a very efficient process resulting in very high yields with only a slight excess of nitric acid/nitrate. Check the stoichiometry or, even simpler, just look at the quantities I used a page back in this very thread.

Trotsky - 18-1-2015 at 18:21

I'm away from my notebook but I can get you numbers if you want. I used 10% excess for the first nitration, and 20% for the second.

I wasn't sure if allowing it to sit in the nitration bath overnight before applying heat would hurt anything. This morning, however, before I went to apply heat I noticed that a mass of beautiful hairlike crystals had formed in it, descending down from a thin layer of the waxy stuff I produced in my first nitration. Obviously impossible to say for certain, but do you think this is just recrystallized MNT or has DNT formed without applying any additional heat beyond that generated when the MNT was added to the bath? I delayed the heating phase because I want to get a good photo of these crystals, they're the biggest I've made of an EM, about 2-2.5 inches in length, but ridiculously thin.

Trotsky - 19-1-2015 at 08:16

From MNT to DNT seems to have failed. The solution turned clear and a small, viscous layer formed on the surface, while small bubbles bubbled up. This was after 2hrs at 80C. Was this because I used AN and not KNO3? Did the AN decompose?

When the solution was poured over ice chips a very light yellow waxy looking stuff appeared and the solution turned milky and opaque, very unlike the clear solution I had before.

The almond smell is gone, but is this waxy stuff DNT? Melting pt test time I guess.


Edit: Actually, hennig, the product I had after.letting the MNT sit in nitration bath over night looked exactly.like your picture number two above. I then took that and heated it to 80C for two hours. Mistake?

[Edited on 19-1-2015 by Trotsky]

TinkerKABOOM - 19-1-2015 at 13:40

Can you add ammonium nitrate,sodium nitrate or potassium nitrate to the nitric acid to make a more stable yet powerful form of RDX?

Metacelsus - 19-1-2015 at 16:10

No. TNT and RDX are completely different, structurally.

roXefeller - 19-1-2015 at 18:45

Ah come on. Throw him a bone. There both cyclic right? Even if RDX is heterocyclic. But to be serious he should really read more before posting.

maleic - 21-1-2015 at 19:40

The most powerful is probably ONC and HNIW now? Whatever, the preparation of these products are too dangerous.



Microtek - 22-1-2015 at 01:05

I wouldn't say that the preparation of ONC or HNIW is particularly dangerous, however, it is difficult and expensive.

Some of the newer articles about energetic salts (eg. bis-dinitroethylnitramine derivatives) indicate a predicted performance that exceeds HNIW and is about on par with ONC.
Of course, this may be a group of materials that the software doesn't model well...

Hawkguy - 27-1-2015 at 21:47

Alright having problems. I nitrated some toluene for two hours at 20 - 25 degrees C. The result is a bright yellow solid, which melts at 30 degrees, is explosive, and forms nice crystals. I thought it was para - mononitrotoluene but the melting point is too low. I have doubts about ortho - mononitrotoluene as well because it sinks... Purification/ ideas on comp?

Microtek - 27-1-2015 at 22:30

Why does its sinking affect your thinking on what it might be? Both o- and p-nitrotoluene has densities above 1 g/cc and should sink. The low melting point is probably because you have a mix of isomers, or otherwise impure product.

Hawkguy - 28-1-2015 at 15:41

Thanks then. How do I purify it? Most comments/ threads about purification are based on TNT, not MNT

Hennig Brand - 29-1-2015 at 08:05

I noticed this a while ago in the prepublications section. It should give you some ideas for how to separate MNT isomers from one another.

http://www.sciencemadness.org/talk/viewthread.php?tid=29111

Hawkguy - 2-2-2015 at 19:02

Hey guys, uh I'm doing some reading into TNT/ nitro - toluene's carcinogenic properties, and the risk/ payoff ratio is sketch to me.... How do you dudes see it?

Hennig Brand - 2-2-2015 at 20:07

Pure alpha TNT apparently has quite low toxicity, however, DNT is apparently very carcinogenic. I just use common sense; limit contact and wash well before eating or using the bathroom, etc.

Hawkguy - 2-2-2015 at 20:37

Yeah but dude: A problem is DNT vapour as well. 2, 4 - Dinitrotoluene vapour is released (By DNT or TNT I don't know), and the dudes use it to locate TNT, buried or concealed. That should indicate that there is more than trace vapour, and potential alpha TNT decomposition among even professional/ industrially prepared samples.

Microtek - 3-2-2015 at 02:14

If you have prepared any nitrotoluenes, it is pretty obvious that mono- and dinitrotoluenes have a relatively high vapour pressure, since they have a very distinctive scent. However, many things that you are exposed to every day are quite carcinogenic (diesel fumes, cigarette smoke, etc.). The poison is in the dose (and, in the case of carcinogenic substances, especially in repeated exposure). I'd say that unless you plan on making TNT regularly over a period of several years, you don't really need to take other precautions than what Hennig does.

Hawkguy - 20-2-2015 at 17:37

Okay so after another attempt at o - Mononitrotoluene, it failed again. Toluene was added to a Nitric/ Sulfuric mixture. What tended to happen was a red liquid would form, dissolve, and precipitate as a beige solid. The temperature would start low and rise to 50 degrees Celcius. Usually I would think it to be obvious 2, 4 Dinitrotoluene, but the reaction temperature seemed a bit too low. This is great

Metacelsus - 20-2-2015 at 18:04

If you're nitrating at 50 C, a lot of DNT will be formed. If you can keep it below 20 C, then you will only get a few percent DNT, especially if you add the nitric acid to a mixture of the toluene and the sulfuric acid, instead of adding the toluene to the mixed acids (so that nitric acid is never in excess).

Hawkguy - 21-2-2015 at 11:32

How can I separate Para MNT from 2, 4 DNT? As well, the stuff is all heavier than water, a waxy liquid, so I think there's some Otho MNT chilling in there too. What a bloody mess. Is there anything I can do?

Trotsky - 22-2-2015 at 22:59

Should be solid at room temp?

Hennig Brand - 16-3-2015 at 04:41

Here is document of interest. It has a graph showing critical diameter of cast Pentolite as a function of percentage PETN.

Attachment: Critical Diameter and Spin Effects in Detonation of Cast and Liquid Explosives.pdf (369kB)
This file has been downloaded 612 times


[Edited on 16-3-2015 by Hennig Brand]

DNT step Attempt

NeonPulse - 22-3-2015 at 03:41

So finally i got around to my attempt at synthesizing some TNT-well DNT actually, havent done the DNT to TNT nitration yet but that will be done as soon as my sodium sulphite order arrives.
So for this synthesis i used 38.5g ammonium nitrate and some %98 tech grade sulfuric acid 85ml, and 11mls dist water,I also acquired some pure toluene,At least the label says that and its density measurement is pretty spot on a density chart i have, its not "diggers" brand. 25mls of this was used.
I followed the a synthesis that was done by fellow SM user Hennig Brand a few pages back for a guideline, mostly because he had success with the method and got some fine looking end product from it although i did scale it down by half.Also i added the toluene to the mixture not vice versa like HB did. The nitration mixture was made the day before and put in the freezer overnight and warmed to 5c before adding any toluene which was done from a glass syringe in small portions at a time The whole process ran pretty smoothly with the temp rising slightly with each addition and upon finishing it was at around 50C. additions were completed fairly fast in 45mins. 15 mins after the last addition of toluene the heating was then applied very gently with a water bath to 80C where it was held for 1hour 45mins. the mixture was then allowed to cool and the DNT solidified gradually with the waxy oily looking cake fished out crushed a bit and washed several times with cold water. upon drowning the spent nitration mix a bit more DNT was recovered also. these were combined and washed again but molten in hot water and agitated for 10 mins and set to cool with the DNT cake solidified in the vessel. It's still yet to weigh it but the yeild loos good.
The pic of the darker layer im not 100% sure of time in the synthesis but the lighter layered picture was just before i stopped heating it.
The smell of this synthesis was not as bad as i expected either. It kind of took me back to being a kid and being made to get out the tin of nugget and polish up dads army boots.....:D

Next step will be the TNT nitration step, and i have enough distilled nitric in the high 90%s for this but it is slightly orange and I would like to know if this is ok for a TNT nitration? or does it need to be cleaned first? looking forward to completing this project in the next few weeks since i have been looking at doing this synthesis for quite a while now.NP

IMG_0099.JPG - 271kB IMG_0085.JPG - 290kB IMG_0083.JPG - 209kB

Hennig Brand - 22-3-2015 at 06:07

Looks good. The one thing I did notice was that you didn't use any excess of nitrate/nitric acid if my calculations are correct. Assuming the AN used was completely dry and 100% pure, which it wouldn't be, the quantities you gave would give 2% excess of nitrate/nitric acid. I think 10 to 20% excess would be better to ensure a more complete reaction. You probably used my quantities, but didn't see where I multiplied by 1.1 to give a 10% excess. Admittedly my post was a little bit hard to follow, and I half intended to go back and make it more streamlined and easy to follow, and post it again, but never got around to it. A little lower yield and more MNT contamination is not a big problem at this stage anyway.

Hawkguy - 22-3-2015 at 19:44

Quote: Originally posted by Hennig Brand  
Looks good. The one thing I did notice was that you didn't use any excess of nitrate/nitric acid if my calculations are correct. Assuming the AN used was completely dry and 100% pure, which it wouldn't be, the quantities you gave would give 2% excess of nitrate/nitric acid. I think 10 to 20% excess would be better to ensure a more complete reaction. You probably used my quantities, but didn't see where I multiplied by 1.1 to give a 10% excess. Admittedly my post was a little bit hard to follow, and I half intended to go back and make it more streamlined and easy to follow, and post it again, but never got around to it. A little lower yield and more MNT contamination is not a big problem at this stage anyway.


It would be useful to have a bit more acid excess. From experience, the best DNT results come from putting MNT isomer(s) contaminated DNT slag through a second nitration to completely synth DNT, and recrystallizing it from Methanol. VERY pure DNT is created.

[Edited on 23-3-2015 by Hawkguy]

NeonPulse - 23-3-2015 at 02:17

So the yield ended up being 30.8g and it is seemingly contaminated with at least some MNT judging by the smell and after drying there is an oily feel left on the glove after touching some of the cake. but i guess you learn things by experimenting so im not totally bothered by the product or the weight of it since this is my first attempt at nitrating toluene. there is obviously room for improvement here and i really just wanted to get a feel for the process and will be trying again when i get a chance. I will be nitrating the DNT/MNT sample further to see what the end product will be like and work on improvements from there. if i use excess nitric and extend the heating time i should end up with an OK end product after washing/purification/recrystallizing with at least some TNT. Working on a Melting point apparatus of some sort may be a good idea and helpful in determining the TNT content of the final sample.

Hennig Brand - 23-3-2015 at 05:52

Quote: Originally posted by Hawkguy  

It would be useful to have a bit more acid excess. From experience, the best DNT results come from putting MNT isomer(s) contaminated DNT slag through a second nitration to completely synth DNT, and recrystallizing it from Methanol. VERY pure DNT is created.
[Edited on 23-3-2015 by Hawkguy]


What is "best" may not always be the same. On an industrial scale where extremely large quantities are made improving yield by even 1% is a really big deal. One percent of a 100g batch is only 1g, but 1% of 100 tonnes is 1 tonne and of course economics is the main factor for the people making tonne quantities whereas for the hobbyist economics is normally a small factor.

I have an extreme sensitivity to MNT, even a couple good whiffs of it will cause the glands in my neck to swell, my throat to get really soar and I just feel awful. It is easy to run the toluene to DNT nitration so that the product produced smells only slightly of MNT and causes me very little discomfort. Also, with a little care the nitration of toluene to MNT can be done quite efficiently. When producing MNT, it can also be very difficult to completely get the smell of MNT off of the equipment that was used, which can be an annoyance for a long time after the synthesis. Also DNT is more useful to me than MNT, so I am producing a more useful intermediate in one step on the way to TNT. The extra handling, especially since MNT is so unpleasant to deal with, just isn't worth the slight economic benefits for me for a number of reasons.

For many uses of DNT, small amounts of contaminants including various other nitrotoluenes is not a big deal. A small amount of MNT going into the final stage of nitration to produce TNT shouldn't be much of a problem either, unless it is a large amount and then the amount of nitration mixture may need to be increased and the nitration may need to be run a little more carefully at least in the early stages.


[Edited on 23-3-2015 by Hennig Brand]

Hennig Brand - 26-3-2015 at 10:24

In the middle paragraph of the last post I wrote, "Also, with a little care the nitration of toluene to MNT can be done quite efficiently." It should have said, "Also, with a little care the [single step] nitration of toluene to DNT can be done quite efficiently."

The following quote and table were taken from the "Detonator Casings" thread. I thought it would be good to include it here.

Quote: Originally posted by Hennig Brand  


I don't want to get too far off topic, but I thought I would include the following jpg of a table taken from an old defense document (Powder and Explosives by A. G. Gorst). It provides some minimum mercury fulminate initiator charge weights for cast and pressed TNT and Picric Acid. As you know, granular TNT and picric acid are much easier to initiate than their cast forms. Very commonly, granular or crystalline TNT or picric acid was used as a booster to initiate cast TNT and cast picric acid.

BTW, did you check the melting point of your TNT? TNT even when of high purity is relatively insensitive to initiation.

TNT does take a bit of time to make, but after doing it a couple of times I find it fairly straightforward and with the right equipment (large flasks, etc) it could be made in large quantities relatively safely. It wouldn't take much longer to make a pound batch than it would to make a 15g batch.



TNT & Picric Acid - Influence of Physical Structure on Charge Sensitivity.jpg - 58kB


[Edited on 26-3-2015 by Hennig Brand]

Hennig Brand - 26-3-2015 at 11:20

Here is another table, taken from the same text, showing limiting charge weights required to initiate TNT, picric acid and tetryl pressed with the same loading pressure in copper blasting cap casings. The difference in limiting primary charge weight, required for initiation, between TNT and picric acid is much smaller than between the two when pressed to practical densities or when cast.

Pressed TNT, Picric Acid and Tetryl Sensitivity to Initiation.jpg - 87kB


[Edited on 26-3-2015 by Hennig Brand]

Correct disposal of "red water"

NeonPulse - 4-4-2015 at 18:24

So I completed a TNT synthesis a couple of days ago and got a fairly good result. I won't go into the particulars of the process too much as it has been discussed quite a lot already on this thread. I'm Now up to the washing/purification stage and will be doing this with a 5-10% hot sulfate solution. The Part that bothers me is a the Environmentally toxic waste so called "red water" containing the impurities and undesirable isomers. For obvious reasons we can't just take this waste to a treatment plant or waste disposal facility and its not really something you would want to store either and since it is pretty much toxic waste flushing it down the drain is out of the question, so what do we do with it? Is there a safe way to destroy the by products and make the solution safe for disposal down the drain? What have you guys done with this leftover garbage? In the past I just watered my garden with the spent nitration acids heavily diluted since plants like nitrates and sulfates.

Hennig Brand - 5-4-2015 at 05:57

I tried using a sulfite wash a couple of times in the past and it was not convenient at all. It actually damaged my product too which I think had a lot to do with the temperature being too high. I found recrystallization from either methanol or ethanol to be much less messy and much harder to do improperly.

There are a lot of articles available giving procedures for how red water can be dealt with, but I never looked into it much because the quantities of waste I produced have been so tiny. I think industrially it has been a big problem and I think most of the options available are less than ideal, either not very effective or very costly or both. Apart from finding a chemical additive which could render the waste less of an environmental hazard I would suggest waiting until you had a good hot campfire or bonfire with lots of hot coals and incinerating it.


[Edited on 5-4-2015 by Hennig Brand]

Hennig Brand - 5-4-2015 at 11:40

Attached are a few patents describing some of the issues and solutions related to TNT purification. I should have read these before trying to perform a sulfite wash earlier on.

Attachment: US3043885.pdf (585kB)
This file has been downloaded 755 times

Attachment: US1975598.pdf (420kB)
This file has been downloaded 564 times

Attachment: US2126162.pdf (329kB)
This file has been downloaded 478 times

Attachment: US2132845.pdf (251kB)
This file has been downloaded 386 times


Bert - 5-4-2015 at 13:39

I recall a process using a toluene extraction to salvage the organics that would preferentially dissolved into the toluene layer to clean up the TNT wash water, then recycleing the toluene & various impurities it contained right back into the next nitro toluenene synthesis. Also mention of harvesting the various TNT isomers/impurities for other processes and desirable explosive products in COPAE, as they represented a loss of fixed Nitrogen & inefficiency if wasted.

It may take me a bit to run down the references.

TNT? DNT?

greenlight - 30-10-2015 at 05:49

I just dug up a two year old batch of TNT/DNT that was made using Jared Ledgers crapbook method.

I have the notes written down and I used 98% sulphuric acid and 70% nitric for all the steps. I have the amounts I used somewhere but I cannot find them at the moment. They were a scale-down from Legard's amounts for the three step nitration in Prep manual of explosives.
For the mononitro step, the nitrating acids were heated to about 43-45 degrees and the toluene added drop-wise from an addition funnel. The mix was then stirred for 20 minutes at about 50 Degrees before separating the layers.

For the second dinitro step fresh acids were heated to 75 Degrees and the MNT dripped in from an addition funnel again. Addition took about 20 minutes. After the addition , the mix was heated to about 85 degrees for 10 minutes and taken off heat with continued stirring and then put in a sep funnel and the top layer stored.

For the final trinitro step, the fresh nitrating mix was heated to about 90-92 Degrees and the temperature maintained while the DNT was added. Addition took about 20 minutes from what i remember. The DNT had to be warmed and melted back down as most of it had crystallized between steps. After this, the mix was kept at 90 Degrees for 5 minutes and then brought up to 112 Degrees for a further 5 minutes before cooling for 5 minutes and crashing into ice-water.

The final product has been bicarb washed and water washed under hot 80 Degrees water about 10 times before being bagged and stored.

Finally, the question, without the fuming sulfuric acid (oleum) do you think I would have got any TNT product at all or could it all be DNT? Is it possible to obtain trinitrotoluene without it?
I will do a melt test tomorrow and see what temperature the product melts at which should give me a fair idea.


[Edited on 30-10-2015 by greenlight]

20151030_210759.jpg - 2.7MB

NeonPulse - 30-10-2015 at 21:16

I think the heating period for the last step is hours not 5 mins and up to 130c in temperature.

greenlight - 1-11-2015 at 08:21

Thanks NP, i will do a melt test anyway to get an idea of the dinitrotoluene content.
After the addition of the DNT, Ledgards total heating time is 15 minutes in his book:(
Looks like i will have to melt it and use a fresh nitration mix with longer time and higher heat to get the third nitro group on. Not a fan of this method as it uses a lot of sulphuric acid.

[Edited on 1-11-2015 by greenlight]

NeonPulse - 1-11-2015 at 15:17

Don't trust anything from ledgards book- it is notoriously full of inaccuracies and dangerous procedures which were poorly researched. You would be much better off deleting it off your hard drive and using the space for something better. There are much more accurate synthesis described in this thread.

greenlight - 2-11-2015 at 09:23

Yeah I made this a couple of years ago using Ledgards book and it is one of the only synthesis i have attempted from it.
I don't use his book as a guide for any explosive synthesis at all now.

greenlight - 3-11-2015 at 10:08

A piece of the product was put in water and the water heated until it melted. Started at 55 Degrees and was fully melted at 60 Degrees.
Very strange, between the melting point of MNT and DNT but nowhere near TNT.

Agari - 9-11-2015 at 17:33

There is a mirror of the Megalomania website on the Deep Web:
nope7beergoa64ih.onion
I stumbled across if by accident while searching "Astrolite Synthesis"(The procedure was very close to what I had thought it would be) using the Disconnect Search engine,the default search engine used by the TOR Browser, which can be downloaded here. In case you are wondering,I use TOR because my other browsers are slower compared to it, and I am too paranoid to simply use the HTTPS version of this forum, especially after the phosgene thread that I posted in Organic Chemistry a while ago.
Just a heads-up, I caught a glimpse of a "cooking" section on the website,though I will not visit it for obvious reasons. I am aware that this post does not necessarily concern the preparation of TNT,but I am simply posting the link to a mirror of the now-gone Megalomania website.
Edit:I think that this belongs in another thread, I will start a separate thread linking the Deep Web mirror.

[Edited on 10-11-2015 by Agari]

NeonPulse - 10-11-2015 at 16:18

Someone has already taken the time to copy the whole TNT synthesis by mega on the first page of this thread about three posts down so there is no need to visit the link.

Agari - 10-11-2015 at 18:58

Quote: Originally posted by NeonPulse  
Someone has already taken the time to copy the whole TNT synthesis by mega on the first page of this thread about three posts down so there is no need to visit the link.

But now we have access to more energetic material syntheses!
Looking at other proposed methods in this thread,we now know which one is the "true" method.

Daffodile - 14-3-2016 at 13:48

Instead of SO3 whatever other route, I added 30ml m-phosphoric acid to my acid mix and DNT. Results look pretty good, except the fumes were worse than normal.

[Edited on 14-3-2016 by Daffodile]

IMG_20160314_134514.jpg - 705kB

[Edited on 14-3-2016 by Daffodile]

[Edited on 14-3-2016 by Daffodile]

IMG_20160314_141014_1.jpg - 792kB

Daffodile - 14-3-2016 at 19:59

Hmm I tried compressing some in foil, and heating lightly. It would just deflagrate, and not detonate at all.

PHILOU Zrealone - 15-3-2016 at 03:57

Quote: Originally posted by Daffodile  
Hmm I tried compressing some in foil, and heating lightly. It would just deflagrate, and not detonate at all.

A few grams TNT or DNT will not detonate from heating confined inside aluminium foil...well maybe if you trow it naked onto a 2000-3000°C molten metal bath...the Al foil will act as insulator before acting as a heat transfer media slowing down heat transfer to your TNT/DNT and thus it may vapourize and burn /deflagrate before detonation.

TNT and DNT are relatively insensitive for such low amounts you need a detonator.

Daffodile - 15-3-2016 at 11:06

I recrystallized the product from Methanol. Strangely, it crystallized in two portions, which I unintentionally separated when I poured the solvent off the first, allowing the second to crystallize separately. The first portion (also the larger one, about 3 times the mass) had a melting point of 81.5 degrees C. The second had a melting point of about 73 ish.

I would highly recommend my phosphoric acid route, even though about 30% yield was lost at some point.

[Edited on 15-3-2016 by Daffodile]

Hennig Brand - 15-3-2016 at 11:41

Sulfuric acid is just much more common and normally much cheaper I think, but yes other things can likely be used. For small scale I guess cost really doesn't matter much. The SO3 was just used to prepare 98% sulfuric acid, which works great to produce TNT from DNT, but is actually pretty difficult, and extremely inefficient, to prepare by simply boiling down lower concentrations of H2SO4 because of loss of sulfuric acid as vapor without proper distillation equipment, water absorption and the decomposition that takes place at high temperatures/high concentrations.


[Edited on 15-3-2016 by Hennig Brand]

NeonPulse - 21-3-2016 at 00:05

Just this weekend I decided to revisit making TNT and the results were much more satisfying than my first attempt. Once again I used a synthesis devised by Hennig brand a few pages back where ammonium nitrate is the nitric source along with good old drain cleaner of around 93% if my density measurement was correct. However this time I allowed for 20% excess unlike my 1 st attempt. I made up the nitrating mixture and let it sit in the freezer for an hour while I attended something else. This time I was much better equiped for the task since last time I just used a beaker with hand stirring.
The nitration mixture was charged into a 1l RBF with two necks, and a large oval stir bar dropped in, a thermometer adapter in one mouth and a pressure equalising addition funnel to the other and turned the tap to slowly drip 50g toluene into the reaction mixture at a rate of a drop a second slowing occasionally to let the temp not rise too fast and go above 55 yet. For the last 10 mls I just let it rise and 10 mins after the last drop the funnel was switched for a condenser to reflux. Heating was started cautiously and slowly to get up to 80c where it was held for 3 hours with a brief period where it crept up to 90 without me realising. This was soon fixed though. I let the vessel cool a bit and transferred the RBF contents into a 500 ml beaker to cool completely and solidify.
A funny thing happened though, the DNT did not solidify and had me worried that I had somehow effed it up even after an hour n the fridge so I decided to use a syringe to syphon the layer into water and this is where it decided it set solid slowly like the hot ice effect. Scooped this out and quenched the acid into water precipitating a little more DNTthis was placed with the cake into about 600 ml distilled water and heated to melt it while strong magnetic stirring was applied to wash it. The DNT cake was allowed to set cool and fished our out of the beaker, rinsed off and dried for weighing. It weighed 75.1 g and was crystalline with small needles and had very little MNT smell to it. The first batch I made smelt quite a bit like MNT and this one does not at all. There was pretty much no smell during nitration either except when I switched to the condenser so it was well contained in the chosen reactor. I will be completing the final nitration in the next week or so and am actually considering making oleum with some phosphorus pentoxide that I have around, that is if I find the time to otherwise it's just going to be a standard nitration mix of concentrated mixed acids.
T

image.jpeg - 1.8MBimage.jpeg - 1.8MBimage.jpeg - 1.8MB

Hennig Brand - 21-3-2016 at 17:02

Nice looking setup! Really good that you are using reflux! I think your yield should be closer to 100g of DNT from 50g of toluene however.

NeonPulse - 21-3-2016 at 23:44

Thanks! it really helps when you have the right equipment for the job.
I did see you got 100g DNT in your earlier post and i expected similar but i guess there was more impurities in my batch that were removed during the washing stage and also i set the cake up onto a few layers of paper towel to wick out moisture and upon leaving it overnight the paper towell was laden with an oily exudation from the cake and i suspect a lot of the extra weight was lost there. maybe there was losses as a result of the extra hour of reflux but that seems unlikely.
but anyway i'm still quite pleased and i must say as far as a synthesis for energetics goes this is quite easy to do and required minimal supervision- just a regular eye on the thermometer and wait. all in all a much better outing than my first attempt

Hennig Brand - 31-3-2016 at 17:20

I have a suspicion that only one mole of nitrate per mole of toluene was added instead of the required two moles of nitrate per mole of toluene. I added the nitration mixture to the toluene while you did the opposite, I think both can work fine though. Unlike esterifications, aromatic nitrations are not equilibrium reactions, so if the temperature and rate of toluene addition were in line nearly all of the first half of the added toluene would be converted to DNT and most of the rest of the toluene addition would be left un-nitrated. The un-nitrated toluene would act as a solvent as well which probably lowered the yield also. This is my theory anyway.
 Pages:  1    3