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Author: Subject: Synthesizing UN with calcium nitrate
grndpndr
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@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
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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
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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
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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
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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
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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
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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]

.....ejuu....................................................................Ffg..............................g.............
JohnWW
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 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
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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
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from The Oklahoma City
Bombing and the Politics
of Terror
by David Hoffman

"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.

.....ejuu....................................................................Ffg..............................g.............
pjig
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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
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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
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 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
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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
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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
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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
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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
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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
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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)

grndpndr
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 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
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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?

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]

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.

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 Sciencemadness Discussion Board » Special topics » Energetic Materials » Synthesizing UN with calcium nitrate Select A Forum Fundamentals   » Chemistry in General   » Organic Chemistry   » Reagents and Apparatus Acquisition   » Beginnings   » Responsible Practices   » Miscellaneous   » The Wiki Special topics   » Technochemistry   » Energetic Materials   » Biochemistry   » Radiochemistry   » Computational Models and Techniques   » Prepublication Non-chemistry   » Forum Matters   » Legal and Societal Issues