Sciencemadness Discussion Board

Ammonium Perchlorate manufacture

dann2 - 6-11-2007 at 15:00

Hello,

Two reads on AP industrial manufactute.
They are a bit old I suppose but good bedtime reading.




Dann2

Attachment: cep1957.rar (90kB)
This file has been downloaded 520 times


dann2 - 6-11-2007 at 15:01

and

Attachment: cep1961.rar (119kB)
This file has been downloaded 483 times


Xenoid - 6-11-2007 at 20:09

Has anybody had any trouble opening these files?

I'm using a Mac with Version 12 Stuffit Expander and it stalls at fig 6.jpg in the first file and fig 24.jpg in the second file.

Regards, Xenoid

DerAlte - 6-11-2007 at 23:01

Xenoid - make sure you add the .rar file type to the downloaded file. Worked for me...

Der Alte

hashashan - 7-11-2007 at 00:00

If anyone wants to use ammonium perchlorate from NaClO4 for pyrotechnic effects he might reconsider that.
You just can't get rid of the sodium that gets caught in the crystaline structure.
Thats why the only way to produce good quality AP is to make BA poerchlorate electrolyticaly and then convert it to AP

zeppelin69 - 7-11-2007 at 08:55

Quote:
Originally posted by hashashan
Thats why the only way to produce good quality AP is to make BA poerchlorate electrolyticaly and then convert it to AP


Whats wrong with perchloric acid and ammonium hydroxide?

woelen - 7-11-2007 at 13:16

That's OK as well, but not everyone has perchloric acid. This is a very expensive chemical, and in my opinion it would be highly uneconomical to make NH4ClO4 from HClO4.

dann2 - 7-11-2007 at 14:48

Hello,
I have problems with both files and I posted them!
I deleted them first time as I realized they were corrupted. I reposted, they are still corrupted. They are OK on my end, somewhere between my pc, scimad.org and back (to a pc) there is a problem.

@DerAlt What do you mean by:
make sure you add the .rar file type to the downloaded file.

The files are viewable here too.

http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/...

http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/...

Dann2

garage chemist - 7-11-2007 at 14:50

Industry also uses perchloric acid for manufacture of ammonium perchlorate in addition to the older fractional crystallization methods from NaClO4 and an ammonium salt, or from other alkali perchlorates.
HClO4 is not as difficult to make industrially as one may think, it is made from NaClO4 solution and a large excess of strong HCl. NaCl is sparingly soluble in strong HCl and precipitates. The filtrate is distilled in vacuum and the HCl gas and azeotropic HCl recycled.
72% HClO4 then distills as the last fraction.
The process is not very practical in the lab since it is difficult to properly recover and concentrate the large amount of HCl gas and azeotrope.

On a lab scale, one could advantageously use a cation exchange resin to convert NaClO4 solution into HClO4 solution and neutralize this with NH3.
Cation exchange, if done correctly, is so thorough that it is used as an analytical method for determination of alkali metal ions, by exchanging them for H+ and titrating that.
You can certainly get pyrotechnic grade ammonium perchlorate from NaClO4 with this method- the yield will be nearly quantitative as well.
The disadvantage is that you can only make rather dilute solutions of mineral acids with ion exchangers. Also, again you need lots of excess HCl for regeneration of the exchanger, but only in dilute form, and you could distill the excess aqueous HCl from the effluent from exchanger regeneration if economic usage of HCl is a concern to you.

Preparative use of a cation exchanger for the preparation of different acids from their alkali metal salts is one of the ideas I have had in my mind for some time, and I have acquired 1kg of Wofatit KPS from ebay.
Brauer uses the ion exchange method to make perbromic acid from perbromate, and also mentions it as a method to obtain solutions of chloric acid from sodium chlorate. A journal reference was given for the latter procedure, which I acquired.
It doesnt actually give a procedure for chloric acid, but contains the general procedure for the preparations of acids with an ion exchanger, and details on how to prepare the exchanger bed, how much sodium a given weight of exchanger can exchange, regeneration procedure etc...
The only problem is that it uses a different exchanger resin (Wofatit KS) than I have, creating the need of obtaining information about the Wofatites (very old product line, one of the first organic resin ion exchangers commercially manufactured).

Preparative ion exchange offers some interesting possibilities, like converting KClO3 back into pure NaClO3 with practically 100% yield and preparing aqueous solutions of numerous inorganic and organic acids from their alkali metal salts.

ammonium perchlorate purification

WizardX - 7-11-2007 at 15:51

NaClO4 + NH4Cl ==>> NH4Cl04 + NaCl

If your looking for pure ammonium perchlorate from the above reaction then ion exchange as stated by garage chemist is the best method.

However, purification can achieved by the use of solvents to a lesser degree of purity with methanol and acetone.

http://www.sciencelab.com/xMSDS-Ammonium_perchlorate-9922929

Solubility:
Soluble in cold water, methanol.
Partially soluble in acetone.
Insoluble in diethyl ether.

Sodium chloride, NaCl is very slightly soluble in dry methanol and not soluble in acetone.

[Edited on 8-11-2007 by WizardX]

hashashan - 7-11-2007 at 23:31

As far as i know its hard to get rid of Na because Na perchlorate is close in sizes to AP. Thats why i thought that Ba perchlorate would be supperior because its molecule is much much larger

Lithium perchlorate

chloric1 - 8-11-2007 at 01:38

I wish I can remember the patent number but there is a patent that talks about using lithium chloride and electrolyzing this until you get lithium perchlorate. This is turn is reacted with ammonium carbonate to precipitate lithium carbonate.

hashashan - 8-11-2007 at 03:02

that is a good idea, I thought about it ... even if ill have Lithium ions they won't do any harm. However Lithium here is 4 times more expensive then Barium.... so ......

chloric1 - 8-11-2007 at 14:42

DAMN IT! :mad: So where are you and why is lithium so high? I mean it is rarer and supposed to be more expensive than barium but not THAT much.

hashashan - 8-11-2007 at 23:57

Im in Israel. Were not rich in minerals.
Besides If ill go to a chem shop itll be about 8 times more expensive.
However barium is quite cheap here ... 4$ for 2 pounds of barium carbonate

garage chemist - 9-11-2007 at 11:22

Lithium simply isnt cheap, even in bulk amounts. The extraction from natural sources is expensive due to the low concentration in all natural sources, and only economic because byproducts can be marketed as well.
Anything below 20$ for 1kg lithium carbonate is a good price, I think. The cheapest technical grade Li2CO3 from a pottery supplier I found was EUR 10,35/kg.


[Edited on 9-11-2007 by garage chemist]

chloric1 - 9-11-2007 at 15:10

garage chemist-Well here in the USA I can get lithium carbonate from a pottery supplier for $7.50 per pound or $35 for 5 pounds. When you exchange the dollar for the Euro and convert metric to American Standard, it comes out to be very close to your cost over there. No advantage over here. I would set up something with hashashen but he is better ordering from Europe or Isreal if the pottery grade is available there.

Lithium Perchlorate patent

dann2 - 9-11-2007 at 19:49

Hello,
Chloric1 mentioned a patent for Li Perchlrorate. Attached below.
The price of Lithium is not so important (if you are making Ammonium Perchlorate) as you will recycle Li. (reduce, reuse, recylce you know, or is that plastic :D)

Anyhow I read somewhere that Lithium salt could be converted very easily into Perchlorate becasue of the very small size of the Li ion. Cannot remember where I read this but it does not seem to make sense to me as the Li is a spectator ion. Perhaps the larger ions (Na, K) physically get in the way more of (Per)Chlorate formation at an anode surface?


Wonder would Li Perchlorate form easily at a Graphite surface?


Dann2

Attachment: litpat.html (24kB)
This file has been downloaded 583 times


vulture - 10-11-2007 at 07:46

If you're after NH4ClO4 for rocketry you might as well settle for LiClO4 if you're making it anyway. Hell of an oxidizer and very high oxygen content.

garage chemist - 10-11-2007 at 09:07

LiClO4 is also soluble in organic solvents like diethyl ether and THF and the solutions are conductive. It is the best salt you can use if you want to explore lithium metal production by electrolysis in nonaqueous solvents.

hashashan - 28-1-2008 at 13:27

Ok guys ... suppose I got a NaClO4 + NaCl + Na2SO4 solution .... how can I get AP from it.
Adding NH4NO3 resulted nothing.
Anyone care to share his experience please

and garage chemist .... what will happen to the ClO4 ? where will it go?

chloric1 - 28-1-2008 at 14:20

Quote:
Originally posted by hashashan
Ok guys ... suppose I got a NaClO4 + NaCl + Na2SO4 solution .... how can I get AP from it.
Adding NH4NO3 resulted nothing.
Anyone care to share his experience please

and garage chemist .... what will happen to the ClO4 ? where will it go?


WTF? Am I missing something here? the ClO4 will go with your ammonium ion. You see ammonium perchlorate is still soluble in 0°C water to the extent of 11% IIRC. That may seem hard to isolate but keep in mind ammonium perchlorate is MUCH more soluble in boiling water. You would be wise to mix equamolar amounts of ammonium salt with your sodium perchlorate and boil down until the solution is a bit hazy. If you used ammonium nitrate then you have no worries as, on cooling, ammonium perchorate will deposit before any sodium nitrate. If,however, you use ammonium chloride remember sodium chloride is only moderately soluble in boiling water so you will have to filter through a heated funnel then cool. In both cases you need to dissolve your crude ammonium perchlorate in a minumum of boiling distilled water at least once if not more to get a respectable pure product.

hashashan - 28-1-2008 at 14:58

@chloric : the ClO4 was refered to garage chemist with the Li production.

now about what you said ... the sodium sulfate and chloride wont interfere? I am worried about the sulfate .. it is as soluble as the AP

chloric1 - 28-1-2008 at 15:44

yeh sorry about that. I forgot to mention your sulfate. It seems you have a real mess:(:(. Your sulfate will deposit right along with your AP. The only answer is to deposit everything you can by cooling and add VERY warm (50°C) acetone,after decanting, to dissolve out the AP and hope for the best. It may take MANY treatments. Methanol should work to.

[Edited on 1/28/2008 by chloric1]

[Edited on 1/28/2008 by chloric1]

hashashan - 28-1-2008 at 15:51

Damn this AP ... I already precipitated the ClO4 as the K salt.
Anyway ... Suppose I make my perch from NaCl .. and then I destroy the remaining chlorate with Sulfite.. So there is no possible way to precipitate the Ammonium salt in a normal way?

Ferrous Sulphate

MadHatter - 29-1-2008 at 03:17

Can you get FeSO4 from an agricultural supplier ? That'll take care of the chlorate problem
for you and it's very cheap(at least here in the US).

hashashan - 29-1-2008 at 03:39

Never seen it in an agricultural supply here .. but I believe It wont cost too much in a chem shop.

btw ... im not so good in potential chemistry ... can anyone please write down the full reaction of reduction of chlorate with FeSO4?

12AX7 - 29-1-2008 at 07:23

6 Fe(2+) + ClO3- + 6H+ ---> Fe(3+) + Cl- + 3H2O

Notice the equilibrium is heavily dependent on H+ -- an excess of Fe(II) is desirable, with enough acid to react all chlorate and dissolve all Fe(III), which requires a low pH. You will want to wash the product with dilute HCl to remove traces of Fe2O3 (although as it acts as a catalyst, it might be considered a beneficial impurity in pyrotechnia?), then mildly basic or neutral water until the pH is neutral.

Tim

hashashan - 29-1-2008 at 08:42

That I already seen
but i meant a more specific formula
as i understand the Cl- is the NaCl but what is the Fe(III) (is it coming in the form of the ferric sulfate?)
and the H+ will be HCl right?

I just never done this procedure and would like some details.

Im sorry if im making a fool out of myself

12AX7 - 29-1-2008 at 10:22

Doesn't matter, sulfate, chloride and alkaline ions are all spectators. You must add them to the reagents when calculating stoichiometric proportions (which is kind of odd to do anyway, unless you know the amount of chlorate to begin with -- you could titrate a sample to determine this). What's left doesn't matter, unless you want to like, evaporate down the solution and recover whatever all was in it. In that case, you'll get a mixture of Na2SO4, NaCl, Fe2(SO4)3, FeCl3, FeSO4 and FeCl2.

Tim

hashashan - 29-1-2008 at 10:49

I wanted to know the final products to know if they are soluble or not.
and to know how to extract the AP out of all that mess. for example the Na2SO4 is one of the guys I wouldnt like to have in my solution... and as I see there is no way to prevent him from coming to the party... right?
So as I see there is no way to get some NH4ClO4 without HClO4 ... right?

12AX7 - 29-1-2008 at 12:19

Well, no... you use enough water to wash everything else out.

If that's more water than the NH4ClO4 dissolves in, then you should consider an aqueous process instead.

I would go with HCl, heat and a big fan. ClO3- gives ClO2 or Cl2 in acidic solution. Basify with your choice cation (NH4+, etc.) and precipitate.

Personally, I am currently collecting crude KClO4, which I will boil with mild HCl in a pyrex vessel, neutralize and wash with cold H2O. This should leave little chlorate and sodium among the low-solubility KClO4, hopefully spectrally pure to the eye.

Ammonium perchlorate isn't as insoluble, but you could start with NaClO4 (solution or crystallized) and work on that. The remaining perchlorate will precipitate, with concentration if needed.

Tim

hashashan - 29-1-2008 at 13:23

HCl is nice ... but it is absolutely unacceptable if the chlorate levels are high.
and all other methods involve N2SO4 in the end?

If so then probably LiClO4->NH4ClO4 would be the ok... however their solubilities are not too different .... anyway guys .. I'm desperate.

12AX7 - 29-1-2008 at 15:03

Then keep running until chlorate levels are acceptable. You might even run until it precipitates NaClO4 on cooling, which appears to be within reach (I don't know how much NaClO3 can be dissolved in the reheated liquor without falling out on cooling).

Tim

hashashan - 29-1-2008 at 15:24

Yes this is a good idea, but I don't have NaClO3 also :) I make the perchlorate right out of NaCl.

I might try to precipitate the chlorate.... but I don't believe that NaClO4 can precipitate out of the solution because it is much more soluble then the chlorate and it will salt out the chlorate

[Edited on 29-1-2008 by hashashan]

12AX7 - 29-1-2008 at 15:39

Ah, but there's still a chlorate intermediate. I isolate it; you don't.

I believe I have precipitated NaClO4, such that chlorate concentration is small enough not to precipitate, while perchlorate concentration is high enough to precipitate on sufficient cooling. I don't think I've precipitated it by forcing the equilibrium with additional chlorate, which does work to some extent in the NaCl-NaClO3-H2O system. The excess chlorate precipitates preferentially.

Tim

Solubilities

MadHatter - 29-1-2008 at 16:46

Hashashan,

The solubilities of NH4ClO4 and LiClO4 are wide enough for the metathesis and precipitation
provided there is a high quantity in the solution to start with.

From CRC, 62nd Edition(1981-1982):

KClO4 ____________0.75 @ _0 C________21.80 @ 100 C
LiClO4 ___________60.00 @ 25 C________150.00 @ 89 C
NaClO4+H2O_____209.00 @ 15 C________284.00 @ 50 C
NH4ClO4 _________10.74 @ _0 C_________42.45 @ 85 C

The potassium cation is useless and the sodium cation provides the widest potential
precipitate range depending on which anion is used.

hector2000 - 17-6-2008 at 12:47

whatis your idea about this method:
http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/...
and
http://www.wfvisser.dds.nl/EN/perchlorate_EN.html