Sciencemadness Discussion Board

semi-automatic nitration

underground - 28-4-2018 at 16:19

I was wondering if there is a way to do semi-automatic nitrations of sugars. What i have into my mind is a machine that can slowly add powders (nitrate salts-sugars) into H2SO4 during a desired period. With a magnetic stirrer and an ice bath, you only need to slowly add the powders, so what if a machine will do it for us :D I don't think so that it will be very hard to achieve, but i cant think any way to do it somehow.

SWIM - 28-4-2018 at 18:54

How about two auger type powder addition funnels with low speed electric motors working the knobs?

The problem is making the semi-automatic chemist who watches the process carefully in case anything goes wrong.



NeonPulse - 28-4-2018 at 19:50

https://www.sciencemadness.org/whisper/viewthread.php?tid=10...
About half way down the page a user by the name of Gnitseretni constructed an auger with a funnel out of cast Al and a printer gear. He made it just for the purpose that you described. He describes it and has photos of it in action. He said that it works well. Honestly though I really see no point since you have to watch it carefully anyway so why not just do the additions manually?

greenlight - 28-4-2018 at 21:22

I would still want to watch the addition myself too with an automated system.

Otherwise you would want some sort of electrical system in place similar to old commercial NG plants where if the temperature goes to a certain dangerous (runaway) level, the entire reaction is dumped into a large water bath underneath.

underground - 29-4-2018 at 15:02

Quote: Originally posted by NeonPulse  
https://www.sciencemadness.org/whisper/viewthread.php?tid=10...
About half way down the page a user by the name of Gnitseretni constructed an auger with a funnel out of cast Al and a printer gear. He made it just for the purpose that you described. He describes it and has photos of it in action. He said that it works well. Honestly though I really see no point since you have to watch it carefully anyway so why not just do the additions manually?


It is well known that ETN cannot be scaled up that good, so with this way you could do multiple small nitrations. Also you dont need the equipment for the nitric acid fumes cause you will be away

[Edited on 29-4-2018 by underground]

Pyro_cat - 30-4-2018 at 13:40

Quote: Originally posted by SWIM  


The problem is making the semi-automatic chemist who watches the process carefully in case anything goes wrong.



CCTV camera

joseph6355 - 1-5-2018 at 09:45

Quote: Originally posted by underground  
Quote: Originally posted by NeonPulse  
https://www.sciencemadness.org/whisper/viewthread.php?tid=10...
About half way down the page a user by the name of Gnitseretni constructed an auger with a funnel out of cast Al and a printer gear. He made it just for the purpose that you described. He describes it and has photos of it in action. He said that it works well. Honestly though I really see no point since you have to watch it carefully anyway so why not just do the additions manually?


It is well known that ETN cannot be scaled up that good, so with this way you could do multiple small nitrations. Also you dont need the equipment for the nitric acid fumes cause you will be away

[Edited on 29-4-2018 by underground]

Why can't ETN synthesis be scaled up?

underground - 1-5-2018 at 17:18

poor yields

joseph6355 - 1-5-2018 at 18:53

Quote: Originally posted by underground  
poor yields

Why exactly? Oxidation?
What is the highest amount of erythritol that you'd use?

[Edited on 2/5/18 by joseph6355]

I imagine that the amount of time ETN stays exposed to unreacted nitric acid increases the amount of ETN oxidized and also the amount of nitric acid wasted. And since temperature must be kept below a certain degree, the addition time is compromised, rendering unfeasible the addition of higher quantities of erythritol.
Is that it?

I've read a patent (US1691954A) from Frank H. Bergeim (see attachment) in which he not only states that his method results in a more stable product, but also eliminates the exothermic reaction by the time of when Nitric Acid is added.
Erythritol can be sulfonated if I'm not mistaken. By adding 4 moles of Sulfuric Acid per 1 mole of erythritol (and also an excess of sulfuric acid), I believe that a tetrasulfate would be formed and then replaced by nitro groups and producing water that would later be absorbed by the excess Sulfuric Acid.
The author says that the process of Nitric Acid addition would not be exothermic. I am personally skeptical about this statement, but I agree that the intensity of the exothermic reaction would be greatly reduced by this method.


Attachment: US1691954A.pdf (98kB)
This file has been downloaded 253 times

[Edited on 2/5/18 by joseph6355]

underground - 2-5-2018 at 14:03

Have you ever tried that method ? I have tried and i got poor yields. Adding the E as a powder directly to the mixture works best for me

joseph6355 - 2-5-2018 at 16:37

Quote: Originally posted by underground  
Have you ever tried that method ? I have tried and i got poor yields. Adding the E as a powder directly to the mixture works best for me

No, I've never tried, but I will.
What was your yield?

Edit:

Reported yields are 88% of recrystallized product according to:
Explosive Properties of Erythritol Tetranitrate
DOI:10.1002/prep.201300121
Page 4 - Yields are given.
Page 2 - The synthesis are described as according to Bergeim method.

US1691954A:
Quote:

The process of claim 1 in which the temperature of the nitrating mixture is maintained at about 40-60ยบ C until the nitration of the alcohol is substantially complete

Longer nitration time maybe?


Second edit. See attachment.
Attachment: 10.1002prep.201300121.pdf (558kB)
This file has been downloaded 575 times

[Edited on 3/5/18 by joseph6355]

underground - 3-5-2018 at 14:39

I dont remenmer the yields but was really low. I tried it 1-2 times and it was the same, after that i never tried again

BTW, that method it is said that works well with PETN, but never tried cause i dont have PE

[Edited on 3-5-2018 by underground]

joseph6355 - 4-5-2018 at 12:30

Quote: Originally posted by underground  
I dont remenmer the yields but was really low. I tried it 1-2 times and it was the same, after that i never tried again

BTW, that method it is said that works well with PETN, but never tried cause i dont have PE

[Edited on 3-5-2018 by underground]

Me neither. PE is quite hard to get your hands on.

I don't understand how they got a yield so high then.

underground - 12-5-2018 at 13:48

A friend told me that an auto fish feeder machine could works as a machine that can add the salt/sugar into the h2s04.I don't know if the rate can be adjusted so it could be useful for this purpose. I have not any experience nor i have ever seen any device like that , so anyone who have work with this device can tell us please if this is going to work ?