Sciencemadness Discussion Board - Synthesizing UN with calcium nitrate

Synthesizing UN with calcium nitrate

Murda - 5-3-2010 at 21:22

Well I new to the forum but not new the high explosives. The synthesis I use for urea nitrate is:

All that's needed here is urea, ammonium nitrate, and some HCl. Two solutions are made - 39.5g of ammonium nitrate in 25 ml water, and 27g urea in 35 ml water (scale up as needed). These two solutions are then mixed, leaving a clear solution of the two. This solution is then heated to 80 degrees C in a water bath. Once the temperature is reached, the beaker is removed from the water bath. Then, 50 ml of 31.45% HCl is added to the solution with rapid stirring and left to steam. This is then allowed to cool with further stirring. Crystals of urea nitrate will become visible in the solution after some cooling has occurred, and stirring is continued. The solution is allowed to cool with further stirring, breaking up the clump of crystals every once in a while. The solution is then placed in the freezer for a few hours, or overnight, and the clump of crystals once again broken up. The crystals are then filtered and left to dry.

I was doing some thinking. Since AN is kind of hard to come by maybe substitute the AN with CN using about 75g of CN and everything else stays the same. But I did some reading in the MSDS of prill CN and the melting point of CN is 45C. Will this pose a problem when heating the solutions to 80C? Also I read somewhere that CN can emit toxic fumes. I can't seem to find it anymore. Let me know your thoughts and I will try the synth tomorrow if everything looks good.

Thanks

chief - 6-3-2010 at 04:06

Well: I never make any explosives (much better sound comes from my electric guitar

, and I need the fingers for that, as well as the eardrums ...

), but:
==> Is the above post bullshit ? Or does it work differently from standard nitration ? Because: So much water involved ...

If it works: Is it good for any other nitrations ?

As I said: Explosives are not my stregth ...

===============

Or is urea-nitrate just some sort of a "salt" (and not a nitro-explosive) ? Then it would be a forced crystallization: NH4NO3 anyhow has a _very_ high molar solubility ... and the addition of HCl would ppt. the compounds ...

With Ca(NO3)2 it would then be the question, if the ratio of its solubility to that of the chloride would be similar to the ammonium-compounds ... : Then it also might work similarly ...

[Edited on 6-3-2010 by chief]

hissingnoise - 6-3-2010 at 04:45

Quote: Originally posted by Murda

Let me know your thoughts and I will try the synth tomorrow if everything looks good.

If tomorrow's synth fails and it might, you'll have to make AN from NH4SO4 and Ca(NO3)2 by metathesis.
It's extra hassle but at least CaSO4 precipitates!
Or if you have H2SO4 you could go straight for HNO3. . .

Rosco Bodine - 6-3-2010 at 06:54

The reaction of hot strong solutions urea and ammonium nitrate and HCl to precipitate urea nitrate is driven by the solubility relatiionships of the reactants and products, and variations upon that process should also work unless the complication arises involving formation of double salts and/or hydrated salts
having solubilities which compete with the desired precipitation of urea nitrate,
in which case a coprecipitate may result instead. Reactions involving substituted potential alternate nitrates and/or acids are worth trying and only experiment will
reveal what works and what doesn't. The only variation which I have tried is
the substitution of H2SO4 for the HCl in the original scheme, and that did appear to lead to a double salt or contaminated precipitate, however there was no further investigation or even confirmation of that result by me. The concentrations of reacting solutions and the temperatures may have to be adjusted and optimized to different figures better suited for variations on the
original process which I shared here in this forum several years ago.

Murda - 6-3-2010 at 09:08

Thanks a lot for the information guys.

@hissingnoise Well I have AN and have gotten the synth to work and produced great yields using AN but It's just a huge hassle to get small amounts. That's why I am trying to tweak the synth a little with a less know nitrating salt which I can get in large amounts. CN around here is quite expensive but it's better than nothing. The reason I am using this synth is because nitric is impossible to come by that is concentrated unless of course I make it myself and yet too valuable for UN. The reason I am tweaking the synth is because I would like to use AN for synths like ETN which are more powerful than UN. It also got me thinking if this synth works with replacing CN maybe it could also be possible with ETN. The only problem I see is that in the CN MSDS it lists H2SO4 as an imcompatibility. Not sure if it would be the same with a CN solution. I bought CN because I think it has great potential. For instance in ANFO mixtures. In this patent CNAN/FO A mixture of 60% AN 40% CN 5.5% hydrocarbon makes a larger diameter than ANFO by itself by over a foot.
I also feel that maybe a mixture like CN/soy might work as well. I just have no where to do my testing since the area I used to test was replaced with some government factory. I have heard CN/NM is stronger than AN/NM. MY CN is from the fertilizer CO yara and they clearly use their CN in their explosive mixtures as seen here. Yara explosives
Someone willing to do some testing? It would make me very happy. I shall try the UN synth today. If I don't return I guess you know what happened...

By the way the melting point of CN being 45C and me heating the urea/CN solution to 80C won't pose any dangers?

Thanks

[Edited on 3-6-2010 by Murda]

[Edited on 3-6-2010 by Murda]

[Edited on 3-6-2010 by Murda]

not_important - 6-3-2010 at 09:55

That's not truly the melting point of the calcium nitrate, the CN is a hydrate and what is happening is that it is dissolving in it's own water of crystalllisation about 45 C. Obviously if you were using equipment to handle solid prills of CN, its converting to a flowing solution might cause problems, if it's already in solution there's no change at 45 C.

The somewhat vague amount of water in the solid CN will make it difficult to measure exact amounts of Ca(NO3)2 needed for use with X grams of urea. You'll need to use enought to be sure to have some excess CN.

Both CaCl2 and Ca(NO3)2 are quite soluble, there should be no problem from that standpoint. Calcium salts form weak complexes with many ammonia derivatives (and water derivatives the alcohols), there are lists of substances that shouldn't be dried with CaCl2 because of this. If urea is one of those there might be yield or contamination problems.

Calcium nitrate is 'incompatible' with H2SO4 because it forms nitric acid and nitrogen oxides as a result of the heat released - the H2SO4 sucking up all the water in the CN prills; nitrogen oxides are not good to inhale.

Murda - 6-3-2010 at 10:01

The CN is about 1/16" prills that will be added to water and heated with the urea solution.

EDIT: So I did the synth and it was different than UN. I'm not sure what I just made but after pulling it out of the hot water bath I noticed very tiny crystals it seemed like and I added the HCL and started stirring rapidly. It took longer than UN but it started forming crystals before my eyes. Only thing is it wasnt the big UN crystals like I have had experience before. They were very tiny like AP. after letting it sit for about 5 minutes I noticed tiny crystals floating just like AP too! But to me it looks like UN to me. It's now sitting in the freezer. By the way I doubled the amount of water and CN but kept everything else the same.
Thoughts? I will keep you updated on if anymore crystals form and have a video as well right after the crystals started forming. I might put it on rapidshare if people want to see it.

EDIT: More crystals have formed. Still tiny and no clumps either.

Thanks

[Edited on 3-6-2010 by Murda]

[Edited on 3-6-2010 by Murda]

Melgar - 6-3-2010 at 19:55

Here's what I think happened: NH4Cl has a lower solubility than UN, so it precipitates out first. CaCl2 is so water-soluble it's exothermically hygroscopic, so I certainly wouldn't expect it to precipitate out any time soon. And UN has a very high solubility, so expect difficulty precipitating that out too. However, calcium nitrate fertilizer is a double-salt hydrate with ammonium nitrate and water, so I think those little crystals you're seeing are ammonium chloride crystals precipitating due to the presence of ammonium nitrate in the original salt. Sulfuric acid would precipitate out the calcium sulfate and probably force the formation of urea nitrate. Or urea sulfate, but probably urea nitrate. That's a lot of salts to be accounting for at once.

Rosco Bodine - 6-3-2010 at 21:22

Why would you think that NH4Cl has a lower solubility than urea nitrate ?
If that were the case then the original synthesis would not proceed in the way that it does, where urea nitrate precipitates from the byproduct solution remaining
and that byproduct is predominately NH4Cl. Are we doing real chemistry here
using stoichiometry and solubility and temperature changes in a deliberate way
hoped to likely produce an intended result ? Can you write the formula for what it is that you are trying to do ?

Murda - 6-3-2010 at 21:43

I was simply trying to replace AN with CN since CN consists of AN to see what happened. There was no real chemistry here. I would however like to discuss the many hidden uses of CN like I mentioned above. Not sure if it's ok to make another topic on this subject though. I think it has great potential and is not a well know explosive.

Rosco Bodine - 6-3-2010 at 23:41

You need to have an understanding of the formulas and weights and the solubilities of the materials you are reacting in order to set up your experiment
and make any sense of the result. If you are substituting a hydrated double salt of Calcium Nitrate - Ammonium Nitrate you should do the math with regards to
label on the bag which should state what weight percentage of the contained Nitrogen is derived from nitrate. It is a requirement that fertilizers state what percentage of the component nutrients that the fertilizer contains. The common
hydrated double salt of CN - AN is probably labeled 15.5 - 0.0 - 0.0 analysis,
based on a formula 5 Ca(NO3)2 - NH4(NO3) - 10 H2O , with 14.4% of the Nitrogen
being "derived from nitrate" and the other 1% "derived from ammonia".
Therefore, per kilogram of the fertilizer there will be 144 grams of Nitrogen derived from nitrate, and the mole weight of Nitrogen is 14.0067, so there
is about 10.28 moles of Nitrogen (and nitrate as NO3) per kilogram of that fertilizer.

The mole weight of urea is 60.06, so about 10.28 X 60.06 grams, 617.4 grams
of urea will be required for reacting with each kilogram of the fertilizer.

The common 31.45% HCl is almost exactly 100 ml per mole and 10.28 moles
or 1028 ml of HCl will therefore be needed.

A kilogram of the fertilizer should dissolve in 450 ml of H2O at room temperature,
and less H2O would be required for hot solutions.

These figures are unverified, as I have not checked the analysis percentages
stated for the fertilizer against the hydration to see if the figures reconcile,
but these numbers should give you a better idea of how to proceed with an
experiment using some ball park numbers.

I just crunched the numbers a bit on this and the stated numbers are pretty close if not exact. A mole weight
for the fertilizer works out to about 1080.49 grams which
contains 11 moles of nitrate expressed as NO3. For that mole of fertilizer as starting material, you would need 1100 ml of the 31.45% HCl and 660.7 grams of urea.

Adjusting proportions for a reaction neutralized by 1 liter of the HCl which is a convenient reference reagent, 982.3 grams
of the fertilizer and 600.6 grams of urea would be required
to balance the reaction. The optimum water content and crystallization procedure and filtering temperature is something which will have to be determined by experiment.

In terms of the conversion equivalence used for substitution
of the hydrated CN - AN double salt, used in the place of AN,
the multiplier is 1.2272 X the AN amount as would balance
the same reaction equation.

Always, you should first do the math ....
then do the experiment. You must do the math first
in order to have a practical knowledge of how much of each reactant is required by theory if the reaction goes to completion for the balanced equation for the reaction,
and to calculate percentage yield for your actual product.
It is those numbers which help you to interpret observations of the experiment and if necessary to adjust the process.

The optimum yield based upon urea will likely not be achieved using a process based on proportions balanced exactly according to theory, because there is a dynamic involving the solubility and pH which affects crystallization
of the desired product. So the balanced equation for any reaction is only a guide and a practical synthesis usually requires some trial and error varying the proportions to
determine what changes tend to drive the desired reaction further towards completion and/or produce the product desired in a form and purity and quantity which is a
compromise against the 100% of theoretical yield that
is only sometimes achieved.

If I recall correctly, because urea nitrate is very acidic, its precipitation is favored by a reaction mixture having an excess of acid, which was used at 11% in excess of theory
based on the urea, while the nitrate was used at about 9.7%
in excess of theory based on urea. If the same adjustments
are favorable for the reaction substituting the hydrated double salt of CN - AN, then the parallel synthesis adjusted
accordingly away from the precisely balanced proportions
would be as follows:

For the reaction referenced to 1 liter of 31.45% HCl being added to neutralize and drive the reaction by excess acidity,

540 grams of urea in 700 ml H2O ( 9 moles urea )

970 grams of hydrated double salt CN - AN fertilizer in 500 ml H2O ( 9.9 moles NO3 )

1000 ml 31.45% HCl ( 10 moles HCl )

At an 84.4% yield which would be the same as for the original process using AN fertilizer, 935 grams of dried UN will result.

Due to the high solubility of the anticipated CaCl2 byproduct,
it may be possible to use even more concentrated solutions
for the synthesis and obtain a higher yield of urea nitrate than by the method using AN as the nitrate. However,
that outcome is uncertain and predicated upon the absence
of any complication involving formation of any competing double salts.

The maximum theoretical yield of 100% based upon urea would be 9 moles of urea nitrate, 9 X 123 = 1107 grams

In the original poster's proposed reaction, the quantities
are correct with the exception of the substitution of 75 grams
of the CN - AN which should be 48.5 grams instead.

[Edited on 7-3-2010 by Rosco Bodine]

Murda - 7-3-2010 at 18:08

Very awesome. Thanks a lot. I'll replace the 75g of CN with the 48.5 and tell you what I get. Whatever I made before had some oxidizing powers. Of course from the CN a 50/50 ratio ?/AL burned like a flare but needed substantial heat to start it. A little sprinkle of AL on the top of the mixture did the job.

Murda - 8-3-2010 at 20:17

SUCCESS!!! I have a video I would like to share with you guys. The crystals aren't as big as when I tried it with AN but it definitely looks like UN. I did however do bigger batches before with the AN but this one was smaller for testing. I will try to filter and dry the UN tomorrow but I will be busy all day and might have to wait the day after. When the UN is dried I will make another video. I am unable to det the UN because I no longer have a "spot". Some government plant is in it's place now. I want to try and substitute AN with CN to synthesize ETN but do not want to be spoon fed. Where can I do some reading on how to figure out the ratio of CN is needed? Here is the synth.

For this experiment I used 5 grams erythritol, 20 grams ammonium nitrate, and 30 ml sulfuric acid (to allow for ~35% excess nitric acid). This can be scaled up.

The ammonium nitrate was added to the sulfuric acid and allowed to dissolve. This was then chilled in a fridge. Once the acids were cooled the erythritol was added in portions with stirring, while keeping the temperature down. Temperature control is generally more of an issue when using larger amounts than this. The mix was stirred for a few minutes after the final addition and then left to sit for about half an hour longer with occasional stirring. This was then poured into about 500 ml cold water and a precipitate was instantly seen to settle to the bottom. After washings with water and some sodium bicarbonate in water, the product was left to dry. 8g is the yield of ETN.

When I figure it out I will report back to you to see if it's right. Only thing I had to change was I had to add an additional 5 ML of water to fully dissolve the CN because no matter how much I mixed it the prills were not getting any smaller. I will edit this post with the video when youtube is done with maintenance.

http://www.youtube.com/watch?v=ozr1C6lL_DE

EDIT: With the synth provided above with ETN to get the syth to work with CN you would have to use 24.5g CN instead of AN. right? Everything else should stay the same.

[Edited on 3-9-2010 by Murda]

hiperion42 - 18-3-2010 at 13:54

interesting

I tried to work out the numbers using kno3 as the nitrate
and a 23% HCL solution.

urea : technical 46-0-0 urea fertilizer.
kno3 : 13(13.6)-0-45

There is 136 g/kg kno3 which is 9.71 moles of nitrogen per kg kno3.

9.71 x 60.06 = 583.2 g urea /kg kno3

23% HCL @ d 1.18g/cm3 = 271.4 g/l
Molar mass HCL 36.46 g/mol

271.4/36.46 = 7.44 mol/l
9.71 moles = 1305.12 ml needed for 1kg kno3

for 1l 23% HCL there would be required 766g kno3 and 446.25g urea

I am not sure if just using more 23% HCL is going to do the trick without having to modify the addition by adding the nitrate and urea to the HCL.
So the yield for one liter 23% HCL is somewhat lower.

Shouldn't it be much lower or am i roughly correct?

Murda - 22-3-2010 at 14:21

From what I have heard kno3 has better yields than using AN with this method. I am unsure though with your concentration of HCL. I was wondering if there any way to confirm UN rather than detonating it.

hiperion42 - 23-3-2010 at 05:08

In any case more 23% HCL will be needed to roughly get in the same range of yields gotten with 31 % HCL.
I can't see any immediate substantial obstacles with the 23% route aside from needing more (HCL).
I will have to test this.

"I was wondering if there any way to confirm UN rather than detonating it."

I don't understand. Can you reformulate please.

[Edited on 23-3-2010 by hiperion42]

Blasty - 23-3-2010 at 06:21

Quote: Originally posted by hiperion42

"I was wondering if there any way to confirm UN rather than detonating it."

I don't understand. Can you reformulate please.

I think that he means if there is a way to test that you have actually produced urea nitrate other than detonating it. In other words: is there a chemical test for urea nitrate?

ScienceSquirrel - 24-3-2010 at 09:27

Urea nitrate melts at 152C

A simple melting point apparatus will suffice to characterise it.

Nice sharp melting point at 152 C to a clear liquid, you have pure urea nitrate!

franklyn - 27-3-2010 at 03:27

Metathetical double decomposition of selected salts wll obtain Urea Nitrate without
the need for liquid acids. I had made these observations
http://www.sciencemadness.org/talk/viewthread.php?tid=7553#p...
http://www.sciencemadness.org/talk/viewthread.php?tid=2642&a...

Urea Oxalate has trivial solubility but heated in a solution of Calcium Nitrate should
exchange ions precipitating Calcium Oxalate which is virtually insoluble leaving a
relatively pure solution of Urea Nitrate.

Mol weights , Urea - 60 , Oxalic acid - 90 , Calcium nitrate - 164

{(NH2)2CO}2 •H2C2O4 + Ca(NO3)2 •4H2O => CaC2O4 + 2 (NH2)2CO •HNO3
. . . . 120 . . . . . . . .90 . . . . . . . . 236 . . Formula weights

. . . . . 4 . . . . . . . . . 3 . . . . . . . . . . 8 . . . .parts by weight

We see Urea Oxalate is formed from 4 parts of Urea to 3 parts of Oxalic acid.
It can even be bought in that ratio for the equivalent of $ 2 a pound , $ 28 total for 14 lbs.
$ 14 for 8 lbs => www.soapgoods.com/Urea-Prilled-Commercial-p-751.html
$ 14 for 6 lbs => www.soapgoods.com/Oxalic-Acid-p-889.html
Ca(NO3)2 •4H2O is
$ 8 for 10 lbs => http://axner.com/calcium-nitrate.aspx

The ratio of 7 parts Urea Oxalate ( mol weight 210 ) to
8 parts Calcium Nitrate tetrahydrate ( mol weight 236 )
is practically stoichiometric. For 15 parts by weight of
materials one obtains 8 parts by weight of Urea Nitrate.
Equal to the weight of Calcium Nitrate tetrahydrate used.

.

franklyn - 2-4-2010 at 21:46

Unless you can buy it in 50 pound bags locally , for smaller quantities this is
as economic as you will find on line , 25 pounds for $ 30 delivered.

http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&item=35026...

.

Murda - 23-4-2010 at 14:58

Not to bring up an old thread. But I read that UN burns vigorously. Mine does not burn but melts to a yellow color. I am thinking it's not UN?

Calcium nitrate or dbl salt?

grndpndr - 15-5-2010 at 18:27

@ Franklyn,Ive made inquiry to the folks(onebay) selling the 'calcium nitrate'
about its being Calcium Nitrate or a double salt Calcium Nitrate/Ammonium nitrate.It is in fact the latter double salt,I was sent a sample and label from the original packaging.EBay Repackaging operation but economical and honest.The other link youve provided
'axner' stocks calcium nitrate terahydrate in its crystaline form rather than
prills and also quite inexpensive though I dont have the price w/shipping at hand.But depending on amounts between.60/80cents a lb less shipping.So far I havent located Calcium Nitrate tetrahydrate as fertilizer
only the dbl salt w/AN.The only places Ive found so far are ceramic supply with the calcium nitrate terahydrate.Or does it make any difference to the reaction?

[Edited on 16-5-2010 by grndpndr]

franklyn - 15-5-2010 at 20:48

Yes , especially on Ebay it certainly is prudent
to interrogate the seller as to composition.
I have not actually done this , but in solution
the chemistry must proceed as expected.
The only questions are the effects of impurties
so recrystallized before is indicated. Then there
is always the issue with temperature versus
concentration. I would just mix as much of
the more soluble salt Ca(NO3)2 as the water
will hold and adding in the required amount of
the Urea oxalate. That prepared in much the
same away by adding the oxalate to a cold
saturated urea solution. Urea sulfate would
also work.

.

Murda - 16-5-2010 at 11:34

Quote: Originally posted by grndpndr

@ Franklyn,Ive made inquiry to the folks(onebay) selling the 'calcium nitrate'
about its being Calcium Nitrate or a double salt Calcium Nitrate/Ammonium nitrate.It is in fact the latter double salt,I was sent a sample and label from the original packaging.EBay Repackaging operation but economical and honest.The other link youve provided
'axner' stocks calcium nitrate terahydrate in its crystaline form rather than
prills and also quite inexpensive though I dont have the price w/shipping at hand.But depending on amounts between.60/80cents a lb less shipping.So far I havent located Calcium Nitrate tetrahydrate as fertilizer
only the dbl salt w/AN.The only places Ive found so far are ceramic supply with the calcium nitrate terahydrate.Or does it make any difference to the reaction?

[Edited on 16-5-2010 by grndpndr]

The yara fertilizer that I bought was not sitting out. She didn't have it but she made a special order for me and had it shipped to her store. In the end I payed around 30 bucks for a 50 lb sack. 15.5-0-0. The only thing she can't get for me is of course AN. all the agri stores around here have urea on hand readily. During the winter months you can also get urea a ice melt

That was the good thing about working at a salt factory. First time I seen about 20 tons of urea.

quicksilver - 18-5-2010 at 10:46

Yara is a very high quality product but they do one thing that is infuriating. They put Mica in the product. This makes it difficult to work on large batches with gravity filtration due to the plunging of the filter medium with the micron size Mica. One a small scale, this is not an issue what so ever.
But if one were to want to pull all the various nitrates on a multi-kilogram scale there would be a need for a very large Buchner Funnel & loose spun glass. Even then the problem would not be completely eliminated. Because in addition to plugging the filter, Mica doesn't "settle down" in the solution easily. The slightest swirl and the crap is moving about.

You COULD attempt to pull the Mica & clay off 1st. By crushing prills, using 60C hot water, the sludge would settle down within the clay. If at that point you were careful enough (or get a very well tuned vacuum hose), you could decant the clear solution and begin work without that headache. A common 5gal bucket should hold enough Kg in solution to make it worth the effort. To work though a 50lb bag may take about a week but you'd get a promising level of ammonium nitrate. However with the HOT water, you're pulling all he nitrates (nothing wrong with that, you paid for them).

Evaporation would yield an enormous mix, but pure on both counts. Using cold water isn't that feasible as it wont drop all the clay down to "hold" the Mica in sediment.

I may just try it and write about what I could get from a specific unit weight, in terms of time vs. yield.

[Edited on 18-5-2010 by quicksilver]

grndpndr - 20-5-2010 at 21:55

@quicksilver,what was the name of the yara fertilizer?The sample sent to me and what they claim is the type there selling
30 35lbs/$ 28 $30 is 'Yara calcinit, solution grade15.5 0 0 19Ca.'
Specifically for hydroponics claimed to be completely soluble.No insolubles in the solution grade descriptions that I could find.I guess the only sure way is to put the sample into solution and whatever the case may be see if theres clay/mica or other insolubles if theres an interest at all? Label leaves No doubt it is a dbl salt however,14.5% nitrate nitrogen,1% ammoniacal nitrogen.

quicksilver - 21-5-2010 at 05:43

Yara is the world's largest chem- fertilizer company. The brand offers are "Bela", "Liva", "Mila", & Vera". They are Norwegian names mean Life, Success, etc.
Yara has plants in South Africa, Israel. & several all over the world. What is typical is the 15.5-0-0 (Liva) calcium-ammonium nitrate. Vera may be all solvable; however I have not seen this. They were tasked with making their product difficult to make explosive. It may be the only "bagged" AN sold commonly in the US & EU as the large firms have switched to selling in truck delivery.
I started to experiment with Yara and found that they employ two mechanisms to defeat explosive manufacture. One is the use of micron sized particulates of Mica, the other is a binder that is similar to cellulose acetate and "white glue" which will plug up just about any filter you can throw at it.
One technique is to work with about a pound and a gal of cold water. The "glue" will float if the material is mixed cold and placed in a 5 gal. bucket. Then it can be drawn off with a simple paper towel or rag. The Mica needs to settle. The clear solution decanted off with great care. It is wise to work with at least one or two pounds at a time instead of any smaller amount. The product as it stands is a poor choice for ANFO but as a source for nitrates, due to it's cost, is a fairly good one. It takes some effort but the return, if done on a large scale, is fairly decent.

A much faster technique is to use Electrolysis with stainless steel for both anode & cathode for approx 1 hour with current levels at over 3amps. That will draw the Mica down and the "glue" away from the solution pretty fast; allowing the experimenter to have a good chance to filter the solution with minimal interference.

EDIT: if used for hydroponics...it may not have all the gunk in it. I am not totally sure. However with that price I'd bet you're right. The "LIVA" is about $25 per 50lb and is what is sold down here. However I think they are mostly at the 15.5-0-0 mark.
Some years back there was a DuPont bagged product (32-0-0) that I have not seen again. It was unique as the prills were not as dense as the common local brands. They would easily crush in your fingers & were mentioned by Jery Hurst as THE prilled AN to buy. The YARA product is what's available now unless you want to pay (minimum) $300 for a delivery and have some place to put free, unbagged prills.

[Edited on 21-5-2010 by quicksilver]

grndpndr - 21-5-2010 at 12:03

considering the cost and hassle the calcium nitrate tetrahydrate
sold by ceramics outfits would be cheaper less hassle.My guess is some pretty extreme heat would be required to drive off the water but as to the calcium nitrate thats free of the other crap
AFAIK since I would doubt ceramics hobbyists/proffessionals would appreciate unknown materials in thier carefully prepped glazing.

Yara seems to be one of the largest fertilizer concerns worldwide.A search reveals that Yaraliva is one of the branchs of the product line (calcium nitrate) Yaraliva includes Calcinit (solution grade) highly soluble, leaving no residue when it dissolves,Tropicote field grade,coated for ease of spreading,not suited to hydroponics/fertigation.Nitrabor, (Field grade) similar to tropicote w/boron added.

I wonder if dissolving several lbs is needed to discover if theres mica /clay in a sample of calcium nitrate AN dbl salt.If it were to be recrystalized any foriegn materials would be left behind
I would think?

[Edited on 21-5-2010 by grndpndr]

quicksilver - 21-5-2010 at 17:21

Well, I usually do several lbs to make it worth my while. So really.....I can't say: you may be right.
I found the best - meaning fastest, most efficient way of getting the goods.
You know the pulp paper they use in grocery stores? It's called craft paper. You get a large section and fold up an envelope that closes upon itself and place the ground prills within & dunk that bastard completely and for several days.... That way the gunk stays there instead of in the solution. The soluble nitrates come on through & there's no mess. That way you can set up several Kg for recrystallization without time consuming fuss. I've tried it with ice water ( below 10C) and came pretty close to all AN.
Hurst once told us that several patents existed to make AN non-explosive. But YARA got several UN (get that one) members to help them set up in their nations for just such an endeavor. It's what really helped them own the market on fertilizers. Most nitrate plants have prilling towers, make HNO3 and often make other products on contract. As many nitrate plants did double duty, they used to just sell off their nitrates (like DuPont) until OK and 911 made the world get to be a more frightened and frightening place. The everyone scrambled to find a bagged product that the standard "lone nut" couldn't do harm with.

grndpndr - 22-5-2010 at 20:45

First rate Idea! Tied in a loosely tied multi layered 'BAG' of cheesescloth maybe?You know the fines that needed filtered better than I!?Whats the N% CAN your using for AN collection. Looked for other soluble high nitrate fertilizers.Yara seems the best/one of best fertilizers around.Yara Krista K
is a soluble near pure KNO3.Waiting for price qoute and shipp.
HAIFA,Champion brands are also first rate.For KNO3, FWIW?

quicksilver - 23-5-2010 at 05:42

I think YARA is all 15.5 nitrates (1st number of 3); I don't think anyone makes a bagged 32 anymore. I got a deal along time ago on KNO3. I got some USP grade (pharmaceutical is certainly reagent grade) 30 lbs for $29 and am still using it.
You can get prilled KNO3 from Greenlight, Grant, etc (stump removers) and they clean up very nicely (98% with nothing but a bit of clay that filters easily enough).

IF you find a hydroponics place that has prilled fertilizer / technical grade KNO3 at $1 a pound or better; I say buy at least 25lbs. That should last Hell of a long time!
IF I remember correctly, one pound of KNO3 + appropriate level of H2SO4, distilled down for nitric acid will yield (approx) 600ml of 1.51 HNO3. That's if you go real slow & carefully; watch your heat, & have a decent condenser on the distillation rig.

[Edited on 23-5-2010 by quicksilver]

hiperion42 - 4-6-2010 at 03:21

In holland they sell Nutramon which is 27% N in the form of NH4NO3 + 4% MgO + 6% CaO.
The water soluble MgO was added to prevent people getting the ammonium nitrate out of the fertilizer.

I got me some haifa prilled KNO3 12-0-42+1MgO.
Does anyone know if the added magnesium salts could hinder or prevent the donation of the Nitrogen derived from the nitrate in the UN synthesis?

[Edited on 4-6-2010 by hiperion42]

JohnWW - 4-6-2010 at 04:34

Quote: Originally posted by hiperion42

In holland they sell Nutramon which is 27% N in the form of NH4NO3 + 4% MgO + 6% CaO. The water soluble MgO was added to prevent people getting the ammonium nitrate out of the fertilizer.

MgO is only sparingly soluble, as Mg(OH)2. Anyway, they could, if they wanted to, simply get rid of the Mg and Ca by adding carbonate, preferably as (NH4)2CO3, to precipitate it out as insoluble CaCO3 and MgCO3. Besides, that amount of MgO and CaO is unlikely to make all that much difference to the power of NH4NO3 as an explosive.

quicksilver - 4-6-2010 at 08:37

In context of using NH4NO3 within the confines of ANFO, I would beg to differ. NH4NO3 when used in that manner and ANFO as a whole is a rather sensitive material in terms of critical element diameter, ratio / proportion, preparation, & detonation. If used as prepared prills, they (the prills) need to be of a certain density level, anhydrous in nature and free from contamination. That is why there was a "blast-grade" & a "fertilizer-grade" NH4NO3. A 10% contaminant level would ruin the explosive: no question. Fertilizer grade material with too high a prill density or too much clay surrounding the prill will not act as an explosive in all but the most unique circumstances.

ANFO requires (at minimum) a 6" diameter blast-hole, must maintain a light prill density, & at least 98.7 purity level (w/ the remainder being a nitrate, etc). The level of fuel oil must never exceed 7% w/ optimum being 3.5-4.5%. ANFO is actually a rather specially prepared material and rather easily ruined. All too often "fertilizer-grade" ANFO simply doesn't shoot. - Place within it an obvious contaminant & it will NOT act explosively.

More research has been done in this area than many others by explosive manufacturers due primarily to ANFO's displacement of higher priced materials & it's financial impact on that industry. Blasting agents must meet certain criteria for complete detonation and some (water gels) actually have less strict dynamics than ANFO.

All too often in the most confidently setup blasts, there exists a great percentage of an ANFO charge that does NOT detonate; even with the best & most well placed boosters or gains charges.

When using NH4NO3 as the nitrate portion of ANNM/KinPak, etc; the material is frequently granular due to the common practice of bringing it's purity up by re-crystallization. NH4NO3 is a bulking explosive & as such there are much better materials to choose from. The issue was financial when the choice was made to utilize it. It was generally supplied as a fertilizer from the acid or ammonia plants at the turn of the 20th century & has always been extremely cheap.

EDIT:
In the writings of Joe Dannenberg through the "Contemporary History of Industrial Explosives in America", there are listed the specific prill density levels, the results of fuel oil testing, & comparisons to various other blasting agents / water gels. Additionally, the ANFO contribution research from Ensign Bickford's "Emphasis on Blasting" illustrate how ANFO must maintain a delicate balance, which is not a simple matter.
In fact, the supply of NH4NO3 is & will always be common place. But the availability of REAL "Blast-Grade" NH4NO3 has tightened as are many materials now. And if prilled; the controls are as substantial as most other explosives.
Additionally: Google Hurst's posts in alt.engineering.explosives from UseNet in the 1990's. ANFO is not an easy proposition if weights exceed a few pounds.

[Edited on 4-6-2010 by quicksilver]

hiperion42 - 4-6-2010 at 13:44

from The Oklahoma City
Bombing and the Politics
of Terror
by David Hoffman

about ANFO bombs

"A bomb like that is not easy to mix. According to Gronning,
You'd have to stir and stir and stir to get just the right mixture for
proper combustibility. And then, if it isn't used immediately, the oil
settles to the bottom and the bomb doesn't go off."

"ANFO is easy to make if you know how to do it," adds Jeffrey Dean,
Executive Director of the International Society of Explosives Engineers,
"but it takes years of experience to work with safely." According to
Dean, "It is almost impossible for amateurs to properly mix the
ammonium nitrate with the fuel oil. Clumps of ANFO would inevitably
fail to detonate."

It makes you think twice about the story the U.S. government sold the people
in which Tim McV. allegedly mixed thousands of pounds of ANFO.

pjig - 6-6-2010 at 09:19

Quote:

Quote: Originally posted by quicksilver

Well, I usually do several lbs to make it worth my while. So really.....I can't say: you may be right.
I found the best - meaning fastest, most efficient way of getting the goods.
You know the pulp paper they use in grocery stores? It's called craft paper. You get a large section and fold up an envelope that closes upon itself and place the ground prills within & dunk that bastard completely and for several days.... That way the gunk stays there instead of in the solution. The soluble nitrates come on through & there's no mess. That way you can set up several Kg for recrystallization without time consuming fuss. I've tried it with ice water ( below 10C) and came pretty close to all AN.

I have been the method of ddbl decomposition to get my A-nitrate out of C-nitrate Yara brand fertilizer. It is a painstakingly long process and lots of prep. (crushing the CN prills in a blender.) . The CN is added to A-sulphate in solution
and the AN comes out when the mix is slightly heated and then filtered.
The bitch of it all is, the crushed solution creates a hard-to-filter mass of goo. I have successfully used a t-shirt to act as the filter. The hours of prep and squeezing the liquid out of the mass is a bitch!

The brand of Yara is CN 15.5-0-0 and 19% CA of which 1% is ammonium double salt. (something like 13% is nitrate).

Are you saying that there is an easier way to this process than what I am doing? It sounds like your talking about CAN not CN., with the paper bag method. I still have to do the dbbl decomposition right?, as there isn't enough Ammonium in this brand to be a double salt to turn it to AN. As far as the paper bag idea, I like it.

Can you explain how you scale this one up and how the bag is placed, and how much excess of h2o do you use? I would like to work with 20-50+lbs at a time not just a few.

quicksilver - 6-6-2010 at 11:25

I MAY have responded to this in a PM rather than on the thread.

When you have you salts separated from the clay & binders, etc, you simply get you ammonia generator (ammonium sulfate fertilizer-grade and sodium hydroxide {Lye}) and run a hose with ammonia gas through your saturated solution.
There you have your AN. The ratio of grams of gas per solution molar weight to weight is a simple thing if you go by what Merck would say (as percentage) of CaNO3 existing in your solution. I actually tried this a few weeks back and it worked VERY well in so far as turning C.A.N. into ammonium nitrate (tech grade). But frankly my proof was just seeing if the final product went into solution in cold water (15C) with no agitation. Was there impurities? Certainly but I doubt it was substantial as CaNO3 takes some warm water and agitation to bring into solution. Try it. It appears to work QUITE well.

Re: the craft-paper method of reducing the crap and getting the existing AN: I just make a simple LARGE triangle fold & submerge in cold water for 24 hours. Withdrawing same, I find all the plugging/clogging material (Mica, clay) left in the envelope with a bit of what appears to be CaNO3 undissolved in cold water.

[Edited on 6-6-2010 by quicksilver]

pjig - 7-6-2010 at 10:58

Quote:

When you have you salts separated from the clay & binders, etc, you simply get you ammonia generator (ammonium sulfate fertilizer-grade and sodium hydroxide {Lye}) and run a hose with ammonia gas through your saturated solution. There you have your AN. The ratio of grams of gas per solution molar weight to weight is a simple thing if you go by what Merck would say (as percentage) of CaNO3 existing in your solution.

This sounds good , i'd like more info via PM if you have the time to do so. I dont my process is delivering the max yield yet, but it is fairly ok for my first couple attempts at it with dbbl decomp.

[Edited on 7-6-2010 by pjig]

quicksilver - 7-6-2010 at 16:17

I always check my PM first as I really don't like to veer off topic and that seems to happen no matter how ridged one is in topic.

A.N. will always be available as it's in the top 10 common chemicals in industry. The issue of adulteration is of course to respond to the abuse of the material but we all know (or should by now) that ripping AN out of all but the most insidious mix is not too tough. The real issue is "is it worth it"?
If you're going to use that as a source of solid alkali nitrate, then by all means; get a fair amount and devote a afternoon to pulling down 30lbs of it & storing it well. If you are going to really use it; there is no sense in playing around with a few pound. A 5 gallon bucket should be just fine & now that it warmer, it's a good time to get it over with & stock up.
I can tell you that as a hygroscopic material, it's a serious pain in the ass. Frankly, if your area has about 15-20% humidity, you better think of using an oven because you would be surprised how tough it is to dry.

Possibly one of the most useful facts is that AN dissolves in cold water (10-15C) VERY quickly whereas calcium nitrate does not. That fact will help a great deal. However CaNO3 is not without it's uses, so all in all a bag of C.A.N. is a productive item to buy. What's more, the way it's setup, it really can't be abused as a quick and easy method to harm the public.
(IMO) YARA was a marketing success. Plain AN fert-grade is still available (by truck) so those agricultural endeavors that REALLY need it - won't be hurt as they likely buy it that way in the 1st place.

pjig - 9-6-2010 at 19:49

UN seems like it is at a disadvantage as a explosive compared to AN ( as in ANNM kinepak). I don't think UN could take its place with out a loss in performance. It would seem to me that UN is better used as a "precurser" in manufacture of other compounds , making it VERY usefull ( as in nitrourea ) . No doubt that UNNM would shoot, but I'd imagine the VOD would be quite a bit lower in comparison to AN.

quicksilver - 10-6-2010 at 05:28

That's a good question; I don't know either. Somehow....I think it may. There's no real reason why it shouldn't as it has more available nitrogen than AN.....But not with the ratios of AN & perhaps it may need to be aluminized. If someone were to test it they would need to be fair in that the testing should not be with any less than KinePak's weights.

pjig - 14-6-2010 at 12:31

I just found a bag of CAN27 in my old stash.... I haven't found a source for that grade of CAN yet. The best and most available is the Yara 15.5-0-0 w/ 19% CA. Have they done away with the CAN27, or is it still available in the U.S. ? This weaker grade of CAN doesn't seem to have enough of the AN present to make a detonatable substance( mixed with a fuel like Aluminium or NM as a sensitizer. )
Would the 15% CAN be a better choice as a double decomp material in making UN or the CAN27? I'd imagine that the CAN 27 would leave more of the dbbl salt of AN in the final mix.

KemiRockarFett - 22-1-2012 at 08:41

What about stochiometric mix of UREA with Ca(NO3)2 x 4H20 combined with small amount of Al ( 5 % ) as it is or in a slurry with AN some thickener and more H20 ( more Al) ? Anybody tried?

quicksilver - 23-1-2012 at 07:58

Here is the patent. Extraction of ALL NITRATES from Yara's product is now simple. If you want step by step details; first rad and study the patent. Approx 1 Kg filtration systems have been examining the technique(s)l for about 2 years now. I have seen them and experimented with them - they work! You actually cannot stop the extraction of nitrates from prilling towers with clay and bulking additives.

Attachment: CAN_coating.pdf (94kB)
This file has been downloaded 896 times

grndpndr - 25-1-2012 at 03:13

Quote: Originally posted by KemiRockarFett

What about stochiometric mix of UREA with Ca(NO3)2 x 4H20 combined with small amount of Al ( 5 % ) as it is or in a slurry with AN some thickener and more H20 ( more Al) ? Anybody tried?

I dont recall where I came across this patent but it may answer some questions 'Calcium Nitrate explosive compositions' US patent 3899374.
What caught my attention was the ratio of CN/AN salts named in the patent are within the range of Yaras hydroponic grade CAN.I take the liberty of specifying hydroponic or solution grade as there seems to be no additives such as the clay/Mica insolubles quicksilver mentions just a clear nitrate salt solution.Along with Yaras
anti hydrcarbon etc prill coatings quicksilvers research discovered.
As I mentioned the CN/AN ratio of Yara calcinit mimicks the range reccomended in the patent.Al is used as a sensitizer, a water
miscible fuel is also used although Urea is not specifically mentioned,Some fuels that are mentioned include glycols,formamide,methanol,ethanol,glycerol.Self explosives are mentioned as well,PETN,RDX,TNT,NC etc in some instances.

Other patents I havent seen may help in the

study+understanding the use of calcium nitrate in energetics.
'Method of making Calcium nitrate explosive composition'US 3816191,'Explosive composition containing Calcium Nitrate'US 3787254/3713917.Blasting Slurry Composition containing Calcium Nitrate and method of Preperation'3660181.

[Edited on 25-1-2012 by grndpndr]

[Edited on 25-1-2012 by grndpndr]

[Edited on 25-1-2012 by grndpndr]

KemiRockarFett - 26-1-2012 at 15:36

Quote: Originally posted by grndpndr

Quote: Originally posted by KemiRockarFett

What about stochiometric mix of UREA with Ca(NO3)2 x 4H20 combined with small amount of Al ( 5 % ) as it is or in a slurry with AN some thickener and more H20 ( more Al) ? Anybody tried?

The first idea was just to use urea mixed with Ca(NO3)2 x 4 H2O and heat this mixture above 40 degrees C to make it melt together, probably the H2N- group will ligand to the Ca 2+ ion. To decrease density for this simple mix add wood meal.
Instead of using urea, someone could use sugar or why not starch as thickener and reductive component. Wood powder to make it detonable. 3-5 % Al powder if possible.

Offcourse it would be good to also put in Al and AN but this chemicals are not easy to get any more since the Brevik idiot eventually false flag Norway event. I am just theoretichian by my self so just gives practical guys ideas.