Nitric Acid Catalyst

[10fingers]

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[This message has been edited by 10fingers (edited July 19, 2001).]

[Bitter]

It's an equilibrium reaction, so you will have to control the temperature very carefully of you won't get any product. Look in chemistry books.

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'Guns will make us greedy. Butter will only make us fat.'

[Anthony]

Don't you also need high pressures? I think this is the same process as one I learned about in school, can't remeber the name, but it was German.

[Jhonbus]

that'll be the haber process for making ammonia.

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A physicist can make a bigger explosion than a chemist ever did
http://www.geocities.com/jhon_bus/

[megalomania]

We have gone over this before..but since we don't have the archives up yet, I shall elaborate since I was just thinking about this yesterday. I will be performing this very experiment (again) in the near future. I moved recently and "misplaced" all my notes http://theforum.virtualave.net/ubb/frown.gif

First of all I found out you can use copper as a catalyst, no need to go all the trouble of getting platinum. Copper sponge and wire is readily available. Second, in my experiments I didn't use concentrated ammonium hydroxide, I just used the grocery store stuff, so it didn't work. I have the information to make concentrated ammonia on my website. All you need to do is heat a spiral of copper wire to red heat in a blowtorch flame (about 5 seconds of heating) and immerse it in the neck of a flask of boiling ammonium hydroxide. Heating the hydroxide will cause ammonia gas to vaporize, react with the wire, and the heat of the reaction keeps it red hot. The product immediatly reacts with air to for nitrogen dioxide, which when bubbled into water makes nitric acid. Now, there are some technicial concerns here, like how to keep a constant air flow with enough oxygen, but I need my notes for that.

Everything needed is available in the stores, no exotic temps or pressures, and it works when done right. The cost of your acid is directly related to the cost of your ammonia.



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[10fingers]

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[This message has been edited by 10fingers (edited July 19, 2001).]

[PYRO500]

the way it is is that the copper is a catalist, and only needs to get hot for a short time, so just get a 12 volt car battery, and run the current through the wire til it gets hot (not very long) the copper wont for copper oxide beacuse the whole point of it is just a catalist, not anything else, meaning: it influences a chemical reaction on a substance without canging its own substance

[10fingers]

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[This message has been edited by 10fingers (edited July 19, 2001).]

[PYRO500]

yes, but you see that the gas in the flask in not oxyagen, it is ammonia coming from the ammonium hydroxide

[10fingers]

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[This message has been edited by 10fingers (edited July 19, 2001).]

[Jhonbus]

We did this in school once for a laugh (pretty yellow flames!) Instead of boiling the ammonia, we bubbled pure oxygen into it, both supplying the oxygen and spraying the vapour up. We used a platinum wire also, we didn't know copper would work!

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A physicist can make a bigger explosion than a chemist ever did
http://www.geocities.com/jhon_bus/

[nbk2000]

It's fairly easy to make anhydrous ammonia. Just boil ammonia solution, pass the vapors through a condenser cooled with ice to remove most of the water, and pass the remaining fumes through (I believe) calcium chloride to remove all the remaining water vapor.

You can then liquify the pure ammonia gas by passing it into a flask cooled with a dry ice/acetone slush. The ammonia boils at (I believe) -40F.

Once you have your pure gas you could pass it through a steel pipe, the inlet tube for the ammonia gas extending into the pipe past air inlet holes drilled in the steel pipe. The copper catalyst is heated and tossed into the pipe immediately before connecting the tube that leads into the water.

The error most people make is trying to pump the gas into the water. BBZZZZ! Wrong. Rather, you SUCK it through the water by using a vacuum source (like a draining jug). This draws the ammonia past the catalyst while drawing in plenty of air and pulling it into the water to form the nitric acid.

Mega, any idea the maximum concentration you can obtain using this process? Or will this form a dilute solution that will have to be distilled to concentrate?

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"The knowledge that they fear is a weapon to be used against them"

Go here (http://members.nbci.com/angelo_444/here.html) to download the NBK2000 website PDF.

[megalomania]

This process can easily yield up to about 120% nitric acid! The nitrogen dioxide reacts directly with water forming nitric acid. When all of the water is used up (100% acid) you get free nitrogen dioxide dissolved in the nitric acid, which can go up to 20%, or 120% acid. This is fuming nitric acid, it can be used for many explosive nitrations, or diluted down to the required strength. No further distillations needed.

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[Cricket]

COOL! Now it seems more interesting, much more. Who would of thought?

[Nitro]

NBK the best ammonia source is NH4CL and CaO
this will form anhydrous NH3 gas.
Alternatively for CaO can used NaOH powder.

[SofaKing]

You can make Ammonium Chloride from ammonia hyroxide and HCl right ?

[megalomania]

Before I stick this in the archive...

I have consulted the modern tomes of chemical engineering to devise a more perfect method of nitric acid creation. I have devised a new system and will hopefully soon build and experimental setup.

I have opted to start by directly boiling store bought ammonia, returning water by cooling in a refluxer, and then drying in calcium oxide (lime). You cannot use calcium chloride, I checked. This method is cheaper, as it does not require hydrochloric acid and sodium hydroxide ($). Furthermore, large quantities of ammonia (generated from ammonium chloride) may be too much for the machine, any excess unreacted ammonia will neutralize the nitric acid, thus lowering yield.

The dry ammonia gas is then passed through a copper pipe stuffed with copper sponge. The pipe is cut into several foot long sections and connected such as to make a "U" type of pattern. There will be no single long pipe this way, it will be easier to heat in this collapsed pattern. The pipe is then set into a bed of hot coals, like a little hibache grill, to get it nice and hot. The exit gas then goes into water.

There is more to this, and it is easier to see than describe. Then there are the problems, hence the need for experiment. First of all, I do not know what temperature this needs to be, or if the coals are going to be too much/little. My info says industry uses 750°C temps and the gas contacts the platinum sponge for 1x10^-4 sec. That temp will melt oridinary solder connections on the pipe, so I may not be able to use more than a foot or 2 of pipe (no U shape). Perhaps the extra length of pipe will make up for lower temps, perhaps it will heat up from the rxn, perhaps it will be too much and cause unwanted side reactions... Second, are the problems of oxidation and moisture. If this does not get dry enough, you will create nitric acid inside your pipe! The copper will not last long that way. I have every reason to believe that a little copper oxide may actually be a better catalyst than pure copper, but I do not know how much.

So, then, anybody have some thoughts on the topic? As an aside, this same system can be used to make formaldehyde from methyl alcohol (formaldehyde-->hexamethylenetetramine-->RDX or HMTD). There may even be more chems that this can make, I am checking.

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For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Explosives and Stuff at http://surf.to/megalomania

[10fingers]

deleting post.

[This message has been edited by 10fingers (edited March 19, 2001).]

[This message has been edited by 10fingers (edited March 19, 2001).]

[c0deblue]

The idea of a "universal" catalyzing reactor is exciting indeed!

Is there any reason the pipe itself must be made of copper? Annealed 316 stainless tubing in the desired diameter would be pretty much impervious and could easily be formed to a U shape using an ordinary conduit bender. This could be packed with the copper sponge, which could be replenished at any time as necessary. Custom SS inlet fittings could be tig welded in for a really professional apparatus.

Initial heating of the copper could probably be accomplished in-situ using a hydrogen/oxygen flame (in a separate chamber) with the U-tube connected as a "remote" flue. This would prevent premature contamination of the catalyst while a balanced gas mixture would minimize oxide formation. A tandem valve would simultaneously shut off the gas supply and admit the ammonia solution, after which the reaction would be self-sustaining.

A good source of ammonia might be the "developer" used in diazo (otherwise known as Ozalid or blueline) copiers. This is nasty stuff - 24-28 Baume is typical - but only requires low heat to produce a steady release of pure ammonia gas (the system used in high speed blueline machines). Price today should be $8-$10 per gallon, maybe less.

Automotive catalytic converters for model years prior to 1982 were single-stage and used only the platinum/rhodium honeycomb. One of these (if obtainable) might be usable as-is, since the convertor shell itself is stainless steel - only the protective shield is carbon steel. Bears investigation.

Do keep us posted on your progress Mega. Proceed with due scientific diligence, but hurry up for cripes sake! http://theforum.virtualave.net/ubb/smilies/smile.gif

[HMTD Factory]

Some input here...I just went through the Ostwald process in an chemical industry book,
the process seem to require a lot of control...It might not be as simple as some of you want it to be. Probably will need more sophisticated plan to realize.

For example, temperature :

Oxidation of NH3 is exothermic but to make the environment favor the production of NO
will need low temperature as possible. Temperature being too low will not activate the catalyst; temperature being too high will destroy NO just produced.

There's also an optimum mixture of air and ammonia ( 10~20 : 1 ). Flow rate of gas must be controlled too.

I can type the whole section regarding industrial Ostwald process if you want to read it but it has to be on monday, I am occupied on sunday.

[c0deblue]

Found this, but it seems to only be the contents section of a comprehensive treatment of the Ostwald process. If anyone can suss out the URL for the rest of this paper . . .

http://www.chemsystems.com/search/docs/toc/97s12toc.pdf

[edit]
Oops . . . this paper may in fact have some decent information (if it can be found), but I was rushing out when I came across it and it sure isn't what I thought it was. Sorry http://theforum.virtualave.net/ubb/smilies/frown.gif

Lesson: "Always make sure brain is engaged before posting."

[This message has been edited by c0deblue (edited March 11, 2001).]

[megalomania]

There is no reason the pipe has to be copper, it just seemed the logical choice, it being a catalyst too. A threaded steel pipe might be better still, it may not need to be welded at all. This isn't a pressure reaction or anything, nor is there a hazard of flammible gas getting out, so just thread may be enough. The reason I suggest using small lengths is ease of adding and removing the catalyst. Also the U is not actually a U but accordian shaped, like on the back of you refrigerator. The total distance of pipe may be 5 feet or more, all wrapped in a small space. I suppose with the threaded steel I could add and remove sections as needed. Wrapped like this it would be nearly impossible to add or remove the catalyst unless it is able to be dissassembled.

If temperature control becaomes a problem, there should be ways around that. The only reason I suggest using coals is ease for me right now. I hope to use gas in time, it is cheaper than charcoal. The use of a gas burner for me is a larger initial investment for what I have in mind. A type of burner used in gas grills spreads the flame out over a wide area, perfect for a bent length of pipe. The pipe can be raised and lowered to get a good temp. Also a copper pipe could be wound around a steel tube. A torch could fire inside the tube causing heating of the copper. I can get a pyrometer to check either way. If my experiments work, I may be able to provide the results in a manner wheras you will not require thermometer devices. Air flow can easily be controlled with an aspirator (I hope so).

I think I have a catalytic converter somewhere. Of course I design my experiments to use materials available to the least common denominator (meaning what I can buy in the store everyone can).

Oh, that pdf article is a big tease. That company wants $35,000 to be able to access it http://theforum.virtualave.net/ubb/smilies/frown.gif Unless a username could be hacked.

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For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Explosives and Stuff at http://surf.to/megalomania

[10fingers]

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[This message has been edited by 10fingers (edited July 19, 2001).]

[nbk2000]

An all copper tube might work, but the reaction produces enough heat to melt copper so you may even have to cool it to keep it from melting. Steel tubing with copper mesh (chore boy pads) inside would probably work just fine. The copper would have to be heated first to get the reaction started though so a propane torch heats the copper and then the ammonia flow started.

If excess ammonia gets into the acid, ammonium nitrate is formed so it wouldn't be a total loss.

Anhydrous ammonia is available in rural areas as a soil fertilzer for pennies a pound (in ton quantities http://theforum.virtualave.net/ubb/smilies/smile.gif) Wonder how much copper that would need? http://theforum.virtualave.net/ubb/smilies/wink.gif

What if a U of steel pipe was made, and enough copper added that, when melted, would completely fill the bottom of the U so that the ammonia gas would have to pass through molten copper to get to the other side of the U. Wouldn't the brief moment of passage be enough to catalyze the change with the reaction keeping the copper molten?

The lack of strong nitric is what's preventing a lot of peoples progress from weak explosives like AP to REAL explosives like RDX, NG, NC, and the rest of the high explosives. With nitric, it's almost as easy as flushing the toilet to make high explosives. Without it, you're forced to improvise weak substitutes like HTH+naptha+Al dust.

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"The knowledge that they fear is a weapon to be used against them"

Go here (http://members.nbci.com/angelo_444/dload.html) to download the NBK2000 website PDF.

[megalomania]

I just found a useful bit of data that may or may not be a bad thing, depending on how you look at it.

Hot copper oxide actually reduces ammonia to nitrogen gas, but it doing so it returns the oxide back to copper metal.

2NH₃ + 3CuO --> N₂ + 3Cu + 3H₂O

Any copper oxide that forms during the making of NO will be converted back to the metal. I doubt that the loss of ammonia to nitrogen will be that great unless you start with oxidized copper. The presence of moisture, and thus copper nitrate formation, may be a way to judge the extensiveness of this rxn. This assumes you start with anhydrous ammonia going in.

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[megalomania]

I have some bad news now. I just happened to be browsing one of my chemistry books when I happened onto a section on reaction rates and catalysts. They had a picture of an experiment using a coil of copper wire to burn ammonia in air. It said the principal products of using a copper catalyst will be nitrogen and hydrogen gas, very little NO will be produced, and that's why they use platinum, which does not break down ammonia. Well that is not the kind of news I wanted to hear. I am now inclined to believe using copper will waste so much ammonia that it could be a very expensive to make nitric acid in the end.

Now where did I put my catalytic converter...

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For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Explosives and Stuff at http://surf.to/megalomania

[10fingers]

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[This message has been edited by 10fingers (edited October 26, 2001).]

[kingspaz]

an alternative method for ammonia generation kills two birds with one stone. mix NaOH with AN and add a little water (few drops). this produces ammonia gas which is fairly dry due to only a drop of water being needed to make the reactants aquarious so they will react. also no heating is required making it even easier to make.

[megalomania]

My car did break down last week, the worthless piece of crap. Time to rip off the cat converter before I sell it to the scrap yard or some sucker stupid enough to pay cash.

To assist everyone (well, me mostly) in performing acid synthesis experiments, I am creating a new section just for all the threads about nitric acid and sulfuric acid. We can all pool our knowledge in a central database until success is achieved. Sound good?

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[10fingers]

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[This message has been edited by 10fingers (edited October 26, 2001).]

[CodeMason]

To make anhydrous ammonia gas, to a glass coke bottle, equal parts finely powdered ammonium sulfate fertilizer and caustic soda is added and well shaken. When water is added, it reacts like this:

(NH₄)₂SO₄ + 2NaOH -> 2NH₃ + Na₂SO₄ + 2H₂O

Ammonia gas will pour out of the top.

[rikkitikkitavi]

1)
(NH4)2SO4 => NH3 + NH4HSO4 at about 100-200 C

2)
NH4HSO4(aq)+ Ca(NO3)2(aq) => CaSO4 * 2H20(s) + HNO3 (aq) + NH4NO3(aq) (by solubility product of CaSO4)

3)
NH4HSO4 + NaCl => NaNH4SO4 + HCl

4)
NaNH4SO4 = > NaHSO4 + NH3 (200-400 C)

5)
2 NaHSO4 => Na2S2O7 + H20 (400-500 C)

6)
Na2S2O7 => Na2SO4 + SO3 (500C+ )

7)
SO3+ H2O => H2SO4 (in 98 % H2SO4)
SO3 cant be absorbed in water only!

all the reactions come from Gmelin Handbook of inorganic chemistry, a very very useful
encyclopedia found in most university librarys

conclusion
From easily orbtained fertilizers (NH4)2SO4 , Ca(NO3)2 and NaCL it should be possible to
produce all the three important acids
HNO3 , H2SO4 and HCl! I have so far only made nitric acid by reaction 2) and tested reaction 3) (it is cheaper and far easier to buy HCl!)

/rickard

[CodeMason]

But then, how would one go about removing the ammonium nitrate from the nitric? I'm thinking H₂SO₄ + 2NH₄NO₃ -> 2HNO₃ + (NH₄)₂SO₄ (s). Thus creating more nitric acid and leaving you with ammonium sulfate to start the process all over again.

[rikkitikkitavi]

distillation of course...It is a drag to filter since the CaSO4 forms very tiny crystals.

that is what I used, to get aezotropic HNO3.

I calculated that the reaction with Ca(NO3)2 and NH4HSO4 cant produce more than 50-55 % acid , if you start with saturated solutions at 20 C. Higher temperature can give higher acid concentration due to higher solubility but NH4HSO4 solubility doesnt increase as much as Ca(NO3)2. Not to mention the problem of having to very thick solutions to mix.

But it could be possible to make, I just distilled the acid out of solution to be sure that I had a clean product.

When you are mixing H2SO4 and NH4NO3 you need to distill the mixture to remove HNO3.

/rickard