Sciencemadness Discussion Board

Nitrated Petroleum

Joeychemist - 8-7-2005 at 12:35

Does anyone have experience with this compound (or compounds)?

I am very interested in this explosive, not because of its power but because of its composition. Surely this Nitrated end product is a mixture of several different compounds! There are many different hydrocarbons and benzene derivatives in common petrol along with other additives to make it run smoother through our engines and to provide better mileage, but what are the main Nitratable compounds which are found in gas?

I got this idea to try it from Mega’s Chemlab, but he just copied most of the info word for word right from PART 2700 (volume 8, P 221) and I do not think it to be correct information anyways. I doubt Mega ever actually even tried this and therefore I do not trust his procedure even though it was copied from PATR 2700.:P

I think that a typo was made in PATR 2700 and that it was meant to be said that 5 parts of fuming Sulfuric Acid are needed instead of”15 parts of fuming Sulfuric” and that erroneous info was then copied by Mega to his Chemlab. I found the US patent 745802 which is referenced (and quoted) in Fedoroff which states that 5 parts of Sulfuric acid are to be employed per every 1 part Nitric acid.

The patent mentions that when mixed with oxidizers like KNO3 of NH4NO3 it makes for a good practical explosive as well as it can also be used as a dye. I will be trying this lab soon and will post my observations and theories then.

Attached is a copy of the patent

Attachment: 745802 Nitrated Petroleum.pdf (125kB)
This file has been downloaded 1027 times

halogen - 9-7-2005 at 06:03

hasnt there been a thread on this already?

Joeychemist - 9-7-2005 at 10:57

No

Joeychemist - 21-7-2005 at 14:26

75ml of 70% HNO3 was added to 150ml of 96% H2SO4 and allowed to cool to 15C, to this was then added 40ml of unleaded petroleum while stirring/swirling at a rate as to not exceed a temperature of above 30C. Very shortly after the first few additions of the gas a red oil-like substance was noticed floating on top of the mixed acids. After the last of the petrol was added the reaction was allowed to continue for ten minutes at a temperature of 30C. A thick layer of the red oil colleted on the top of the spent acids.

The entire contents of the reaction vessel were then crashed into 1000ml of ice and water. A bright blood red semi solid product which is very wax-like floated to the bottom of the beaker and was sucked up with a syringe and washed in several portions of water and bicarb solution and then was placed in desiccator for a few hours to remove any residual moisture. The final yield is 28.5ml of Nitropetrol.

The Nitrated product burns quietly while black smoke is produced. This stuff stinks, like, I mean it really STINKS! The end product smells 10X worse than the gas which was used to make it. I carried out the synth under a good fume hood but others in my house still complained about the smell and how it was giving them headaches, but I was not affected by this. Anyways, do this procedure outside if it is possible to do so.

28ml of Nitropetrol was mixed in with 150g of finely powdered Ammonium Nitrate so that the two were very well mixed (the Nitropetrol coats the NH4NO3 very well and has a sticky wax-like consistency to it), then charged into a large aspirin bottle and tamped firmly. The charge was fully DDT with a base charge 0.5g PETN and a mix 0.4g of DDNP/KClO3 (70/30) as the igniter charge.

Next week maybe I will make a main charge of only Nitropetrol and maybe I will try to dissolve some gun cotton in it too.

Back to the original Q; what the hell is in this shit??? I think that the only compounds which are Nitratable would be those of the aromatic group such as Benzene, Toulene, Xylene and so on. But if that is fact then it would seem more logical to mix Benzene, Toluene and Xylene together and attempt a nitration like that.

I’m sure we are all aware that most Aromatic compounds require concentrated acid to achieve higher degrees of Nitration. Also, most Aromatic compounds are not easily nitrated, and require higher temperatures for the introduction of new nitro groups to the Benzene ring than the previous one does. I think that a higher degree of nitration may be possible with stronger acid, and higher reaction temperatures, but! The patent states that if the temperature is allowed to rise too far above 30C that there will be black decomposition products formed, I am thinking this is because of all the other crap in the petrol decomposing.:o

[Edited on 21-7-2005 by Joeychemist]

Slight confusion in the use of words

Lambda - 21-7-2005 at 16:16

Joeychemist, can you please enlighten me on the following:

The American gasoline, similair to the European Petrol, German benzin, Dutch Benzine or Octane fuel. This is sold here as un-leaded fuel.

Petroleum, similar to the European Diesel, Petroleum, Kerosene (jet fuel) and French Gas-oil.

Paraffine, being inbetween Petroleum and Petroleum gelly or Vaseline.

Petroleum gelly, similar to the European Vaseline.

In Europe we allso have LPG (Liquified petroleum gas) wich is similar to liguidfied Pentane.

These things can easily be looked up, but I find the international use of words very confusing. I will therefore like to know from you, exactly what you mean when talking about Petroleum and Petrol.

Joeychemist - 21-7-2005 at 16:29

I'm (particularly) talking about the super expensive stuff that I put in my truck :P Just plain old unleaded gasoline. But others have mentioned using other Petroleum products too.

12AX7 - 21-7-2005 at 16:48

Who knows what it might be. You'd probably be better off taking it to a lab and having them analyze it. Surely oil companies already do this, but I'm sure you'll be damned if you find one. MSDS might show a list, but it may also be ambiguous, i.e. "petroleum distillate" (..no shit..). It also varies by season!

Tim

Lambda - 21-7-2005 at 16:58

Got yah bro !,....so you used the Octaine distilate in your experiments. Man,....I am sounding more American by the day.

Thank's Joeychemist for clarifying this.

Trotsky - 2-4-2013 at 12:04

I have tried this with kerosene, and despite being perfectly clear, it rapidly turns to a red, waxy color as described by the initial report. However, upon addition of the ice water, immediately three layers were formed, a blood red layer on the bottom (small), a large milky yellow layer in the center, and a perfectly clear layer on top. There were a few blobs of red stuck between the clear and yellow layers, I assume just trapped there, not actually different from the layer on the bottom.

I suspect there are many mono-nitro products contained within and that following the procedure laid out for aromatic nitration, solid more highly nitrated naphthalene and alkyl benzenes would appear.

[Edited on 2-4-2013 by Trotsky]

Trotsky - 3-4-2013 at 23:14

After allowing it to sit for 36 hours, the mixture resolved itself into a small clear layer on top of unreacted kerosene, a thin layer consisting of some red liquid and mostly weird noncrystalline waxy yellow-brown material, the largest layer of almost clear spent (but not neutralized) acids, and another layer at the bottom that looks to be more of the waxy yellow brown material trapped above the water layer. Maybe it's different, I don't know, I haven't had time to seperate them.

Some waxy material was removed and tested for burn. It burns very poorly on foil, just melts and smokes like mad. This is about what kerosene does, too, so not too surprising. It's almost impossible to get to burn unless it's on some sort of organic material, so I put some on some paper towel. This burnt like crazy- it doesn't deflagrate as one mass however, instead there are hundreds of small pops of intense flame.

It is definitely shock sensitive, hitting a small amount with a hammer resulted in a definite crack, but given the amount of material, used, it was hardly impressive.

I'm thinking that this might make for an excellent somewhat more sensitive alternative to ANFO. It's obviously oxygen deficient, but sensitive enough that I'd be shocked if an AN/Nitrokerosene blend didn't undergo DDT when confined.

Trotsky - 4-4-2013 at 23:37

Attempts to burn this material under confinement were met with frustration. It seems that it's so oxygen deficient it cannot maintain combustion without significant atmospheric contribution.

Should be good for combination with AN.

The shock sensitivity will hopefully make it possible to make a bullet sensitive ANFO alternative.

jharmon12 - 17-4-2013 at 06:00

So has anyone actually set this off with a cap (by itself or with AN)? It seems that people are making it, but not trying to detonate it.

AndersHoveland - 17-4-2013 at 10:23

I found this, "nitrated petroleum", I do not know if it works, and am unsure about the chemistry. My guess is that petroleum can only be nitrated to a small extent before degrading and being oxidized:
Quote:

This explosive procedure intrigues me because what chemical can be more reliably available than gasoline, or for that matter motor oil, kerosine, and diesel. The nitration of petroleum generally produces either brown non-crystalline solids or liquid products that are explosive. The first attempts to nitrate petroleum were made in Russia at the end of the 19th century by one Dr. Konovaloff. Dilute nitric acid under pressure was used to nitrate the product, obtaining very low yields. In 1902 a nitration method patented by Edeleanu and Filti used mixed nitric-sulfuric acids, unfortunately for them no practical application of their patent was found. Others tried using different kinds of petroleum like A.S. Flexer, Freund, and Kharichkov to name a few. You may experiment yourself on everything from crude oil to kerosene.

Standard gasoline is added gradually to a mixture of 15 parts 100% sulfuric acid and 3 parts 100% nitric acid in a large beaker. Add 1 part of gasoline per 18 parts of mixed acid. The reaction temperature should be somewhat cool, never let the temperature rise above 80 °C. A temperature below 20 °C should do, you can regulate this with a salt-ice bath. When the nitration is completed, the mixture is diluted with a large quantity of cold water to precipitate the product. The un-nitrated oil will float to the top of the acid-water solution. Collect the precipitate on a filter and wash with water, yield will be 30% to 90% depending on the crude oil used to manufacture the gasoline. You will need a graduated cylinder for measuring liquids, and a thermometer to monitor the temperature.


One more note, it might be that this type of nitration worked much better on the old petroleum fuel, which contained substancial ammounts of benzene and toluene. As most of the literature on the subject is very old, this procedure may have worked better a hundred years ago, but may not work so well now because benzene additives have been legislated out of existence, and the gasoline of today is much different than how it used to be.


In general, however, I have read that nitration of alkanes with mixed acids is very problematic, and in general not feasible, except for the higher chain alkanes.

Apparently the nitration of alkanes generally requires special nitrating agents:
Quote:

Nitration of Alkanes using Nitronium Hexafluorophosphate:

Nitronium hexafluorophosphate (3.82 g, 20 mmol) was added under dry nitrogen into a flame-dried 50-ml reaction flask equipped with a magnetic stirrer, condenser, nitrogen, and alkane inlet. Dry dichloromethane (20 ml) then was added, and the appropriate gaseous alkane was passed into the suspension at ambient temperature with rapid stirring. The reaction mixture was monitored by analysis of periodically removed samples. Introduction of the alkane was stopped until the yield of nitroalkane did not increase further. The reaction mixture then was quenched with water and extracted with dichloromethane. The organic layer was washed successively with 5% aqueous NaHCO3 solution and water, dried over MgSO4. After evaporation of the solvent, the nitro product yields were found to be based on the amount of NO2+PF6− used.

NO2+ PF6− is much preferred over NO2+ BF4− as a nitrating agent because it is substantially more soluble in dichloromethane (about 4 mol%), the latter is practically insoluble in dichloromethane. In nitroethane the solubility of NO2+PF6− is more than 25 mol%. (Olah)

Nitronium hexafluorophosphate was prepared from fuming nitric acid, anhydrous HF, HPF6 (60%), and PCl5 following a recently developed procedure (G.K.S.P., D.K. Padma, P.R., D. Adamson, and G.A.O., unpublished results).


[Edited on 17-4-2013 by AndersHoveland]

Trotsky - 18-4-2013 at 16:16

I don't know what the size of alkanes in standard gasoline is, but the kerosene I nitrated is almost solely C11 to C16 alkanes with >1% aromatics. I got about a 38 to 45% yield. Gases were constantly being released, even when stored under water and as such my yields appear to have decreased with time.

The rest was recaptured as unreacted material.

The waxy substance that was obtained was blended with AN at a ratio of about 94:6 (AN:NK)

It was saved in a pill bottle. A roughly straw-sized hole was drilled down the center, filled with NS. A 1/2" layer of AN/NS blend was packed loosely on top of this. I expect .5g of TATP or perhaps ETN would do the job.

The AN/NS layer is there to act as a booster for the much more tightly packed ANNK blend.

After considering the expansion of gasses I added 10% water to the ANNK. Knowing the huge volume expansion from water to water vapor, I believe that this will increase the power.

This will decrease the sensitivity substantially, I believe, correct? I know water has been added to AN for a long time but I admit I have not looked into it's effect on decreasing the ability to initiate detonation.

I had hoped to check the ANNK blend for susceptibility to bullet initiation, but I don't have all that much and I didn't want to waste it.

I once tried to initiate wet pasty tatp with a .22lr in a pill bottle and only succeeded in spraying wet tatp around, so I've always been a bit leery of bullet initiation (though I've never had it fail with tannerite and a .223- I would have figured that a .22lr even if it were subsonic by the time it impacted would have been more than enough to detonate tatp even if it were sitting under 6 inches of water.)