Sciencemadness Discussion Board

Hydrogen Peroxide Production

Fashist - 24-8-2008 at 00:48

hi,
i have various information about H2O2 Production but these patent has no instruction for making H2O2 and didnt descript Well.any one can help me about better plan and instruction for Produce?

Picric-A - 24-8-2008 at 01:41

Hydrogen peroxide is either extremly dangerous or very difficult to produce in a home lab.
It can be made by autoxidation of 2-ethyl-9,10-dihydroxyanthracene to 2-ethylanthraquinone and the desired hydrogen peroxide using oxygen from the air. This is the Riedl-Pfleiderer process. This is the difficult method.
Alternitivly you could try electrolosis of sulphuric acid soloutions followed b hydrolosis of the persulphate ion to H2O2 and then distill it to produce htp (dont ever try this at home! distilling hydrogen peroxide is extremly dangerous and will likly lead to HUGE explosion :))

Klute - 24-8-2008 at 03:42

I don't think distillation of H2O2 from persulfuric/sulfuric acids is even possible, even with moderate vacuum, as decomposition to oxygen will be very quick. Theses solutions are only stable for a few hours at RT, constantly evolving O2 bubbles. Seeing how RT pirhana reacts with any organic matter, I cna't imagine what it will do when hot!

I think electrolysis methods would be more approprite, although this is just a hard guess, I haven't seen any exact procedures as I wasn't really looking.

ScienceSquirrel - 24-8-2008 at 04:43

The most practical method for making hydrogen peroxide at home is the old industrial process of roasting barium oxide in air to form barium peroxide.
The barium peroxide is reacted with cold dilute sulphuric acid to form hydrogen peroxide and barium sulphate. Filtration removes the barium sulphate leaving a solution of hydrogen peroxide.
In the industrial process the barium sulphate was recycled to produce more barium oxide etc.
I am not suggesting making large quantities by this method. But it is an effective lab scale method for making small quantities of a dilute solution

[Edited on 24-8-2008 by ScienceSquirrel]

Formatik - 24-8-2008 at 06:33

Not as insoluble, but in place of barium peroxide, at least CaO2 could also be used. MgO2, ZnO2, SrO2 can also work, but the first two give soluble sulfates. Gmelin ref below p. 2158 mentions that the dilute solutions made from peroxide and acid contain impurities when evaporated and concentrated can cause explosion. So these solutions have to be distilled over at low conc. (30%) leaving behind the residue, a further concentration can be done harmlessly, etc.

There are quite a few ways to form and prepare H2O2. Autoxidation of dilute aqueous N2H4 solutions or alkaline solutions of a hydrazine salt with air (actually bubbling in the air is better) also forms H2O2,e.g. at 25 deg. bubbling O2 into 0.14 m-N2H5OH solution after about 100 minutes decomposes about 0.05 Mol N2H5+/L, and the conc of H2O2 climbs to 0.022 Mol/L (Gmelin O [Sys. No.3] pg. 2140).

The process of the autoxidation of quinones is not hard if you can get the ingredients, e.g. shaking alpha-anthrahydroquinone in an aqueous 5 n-NaOH soln. with air for 2-4 minutes, gives next to anthraquinone considerable amounts of H2O2, where using 0.25 n-Ba(OH)2 instead of NaOH causes the quantitative reaction with the H2O2 in the form of BaO2 precipitate. What is considerably harder, is the formation from alcohols or aldehydes. Electrolysis of conc. K2CO3 solutions at up to 0 deg., forms potassium percarbonate (Specielle Elektrochemie by Heinrich Danneel (1903) p. 116-118), which can likley be used to form H2O2. But then again, electrolysis of sulfate solutions can be used to form H2O2 (Kirk Othmer Encyclopedia, Vol. 13, p. 23).

[Edited on 25-8-2008 by Schockwave]

watson.fawkes - 24-8-2008 at 09:11

Juan Lozano, the fellow from Cuernavaca, Mexico with the homebrew jet pack and now a start-up company, built his own hydrogen peroxide plant. Photo 9 (of 10) of this article has a picture:
        http://www.popsci.com/gear-gadgets/gallery/2006-02/backyard-rocketeer
I don't know what process he used.

kclo4 - 24-8-2008 at 09:24

Sorry, I only skimmed over this, but I didn't see it mentioned, if it was, I am sorry.
Ozone can be produced a bunch of different ways, and then can be used to make Hydrogen peroxide.
http://en.wikipedia.org/wiki/Ozone#Production
Personally the Corona discharge method doesn't seem that bad.

But for a chemical that is easy to get, it would be a lot of work to make in worthy quantities.

kilowatt - 24-8-2008 at 10:16

Quote:
quote]
The barium peroxide is reacted with cold dilute sulphuric acid to form hydrogen peroxide and barium sulphate. Filtration removes the barium sulphate leaving a solution of hydrogen peroxide.

What about cold not-so-dilute sulfuric acid?

Formatik - 24-8-2008 at 15:34

Quote:
Originally posted by Klute
I don't think distillation of H2O2 from persulfuric/sulfuric acids is even possible, even with moderate vacuum, as decomposition to oxygen will be very quick. Theses solutions are only stable for a few hours at RT, constantly evolving O2 bubbles.


Kirk Othmer describes the extraction, where the cathodic reduction of O2 from an alkaline electrolyte gets H2O2 directly, it’s extracted by neutralizing then distilling or forming an insoluble metal peroxide (like one of those mentioned above). Being an overview of H2O2 production, this document has more references on the Weissenstein process.

[Edited on 24-8-2008 by Schockwave]

ScienceSquirrel - 24-8-2008 at 17:41

Quote:
Originally posted by kilowatt
What about cold not-so-dilute sulfuric acid?


Generally hydrogen peroxide has to be generated in dilute solutions.
Strong acid, heat etc cause decomposition of the hydrogen peroxide or the production of unstable mixtures eg piranha.
The dilute solution is then concentrated using special columns.
35% hydrogen peroxide is fairly readily and cheaply available, at least in the EU.
I have never needed hydrogen peroxide stronger than this and I regularly dilute it down for reactions.
It has to be said that distilling hydrogen peroxide is far more dangerous than distilling nitric acid.

ScienceSquirrel - 24-8-2008 at 18:36

Quote:
Originally posted by watson.fawkes
Juan Lozano, the fellow from Cuernavaca, Mexico with the homebrew jet pack and now a start-up company, built his own hydrogen peroxide plant. Photo 9 (of 10) of this article has a picture:
        http://www.popsci.com/gear-gadgets/gallery/2006-02/backyard-rocketeer
I don't know what process he used.


From the pictures and description I would guess that he is distilling a commercially available peroxide solution, probably 30 - 35%.
I really cannot advise this;
1) Hydrogen peroxide in concentrations greater than 35% may be illegal in your jurisdiction without a license.
2) Distillation of hydrogen peroxide is a risky procedure.
3) Dropping really concentrated hydrogen peroxide (> 80 - 90%) on clothing and paper will cause them to spontaneously catch fire.

watson.fawkes - 25-8-2008 at 11:39

Quote:
From the pictures and description I would guess that he is distilling a commercially available peroxide solution, probably 30 - 35%.
Since I posted this I found out that this fellow is selling these stills commercially.
        http://www.tecaeromex.com/ingles/destilai.htm
From this page I summarize a few points.

ScienceSquirrel - 25-8-2008 at 15:43

A great bit of kit and if you have a use that justifies the cost of purchase, obtaining clearance from your local fire and police services and your insurers then go ahead.
I have chemicals and kit and my activities are declared.
My experiments are related to inks and dyes and demonstration experiments at parties etc.
I really could not explain the need to make 99% hydrogen peroxide at my next plod chat.

watson.fawkes - 26-8-2008 at 08:40

I'm not exactly encouraging folks to go build their own stills to concentrate 3% to 35%, but if they're going to, it's going to be a fairly serious project to get something like the TAM still. It's not something to cobble up together with labware unless you've got experience with vacuum systems, electronic heat control, etc.

I don't know anybody that need 98% hydrogen peroxide unless they're making rocket fuel.

ScienceSquirrel - 26-8-2008 at 08:57

35% hydrogen peroxide is readily available in the UK and the US so I do not see much point in concentrating 3% hydrogen peroxide if you live in these places.

Is there anywhere you cannot buy 35% hydrogen peroxide?
It is quite commonly used in the food industry so a bit of sniffing around might be needed!

h2o2guru - 26-8-2008 at 09:00

It's fairly easy to "make" your own peroxide but there's a lot of energy involved. I made a small electrochemical cell to make peroxide using a " trickle bed reactor" got ~2% .

it's also simple to sparge your peroxide to whatever concentration you wish.

But there are a lot of amp/hours involved in a liter of 50%H2O2

Ritter - 26-8-2008 at 09:06

Union Carbide produced peracetic acid using 30+% H2O2. The dilute H2O2 from this process was returned to a distillation column where ethyl acetate was added & the H2O2 concentrated by distilling off the water as the ethyl acetate azeotrope.

I was told about an accident they had where the peroxide concentration sensor failed & the column got to the point where it was at least partially filled with 99+% H2O2. The resulting explosion launched that column into the next county.

watson.fawkes - 26-8-2008 at 12:01

Quote:
Originally posted by ScienceSquirrel
35% hydrogen peroxide is readily available in the UK and the US so I do not see much point in concentrating 3% hydrogen peroxide if you live in these places.
Unless, that is, your interest is in industrial chemistry. In such a case learning how to do the concentration is the whole point of the activity. That said, it's an expert-level project to do. And speaking of lack of expertise:
Quote:
Originally posted by Ritter
I was told about an accident they had where the peroxide concentration sensor failed
Note the indicator of uniqueness "the" in this statement. I have to say, anybody who builds something with such potential hazard as a hydrogen peroxide still with such a single point of failure (that is, lacking redundant sensors) is exhibiting something other than expertise. Perhaps bean-counting, perhaps inexperience... well, those are the most charitable cases I can think of.

kevin.07 - 27-8-2008 at 16:31

Something from someone who knows not alot,
Sodium Percarbonate + Water + Distillation ?

Klute - 27-8-2008 at 16:54

Sodium carbonate + O2 :)

kevin.07 - 27-8-2008 at 17:01

Doesn't oxy radical hook up with H2O?

Klute - 27-8-2008 at 17:31

Yes, H2O2 is formed to some extent, but quickly degardes to O2 and H2o when you heat the mixture.

ScienceSquirrel - 28-8-2008 at 02:44

I think you probably could make hydrogen peroxide from sodium percarbonate by dissolving it in water, adding the calculated quantity of sulphuric acid with cooling to neutralise the base and then vacuum distilling.
It would have to be done on a large scale to make it worthwhile and would be quite expensive.

[Edited on 28-8-2008 by ScienceSquirrel]

Formatik - 5-9-2008 at 13:05

Here's one on the formation of H2O2 by combustion (Ber. 33 [1900] 1109) of an H2-flame which is put onto H2O so it spreads out over it, or better a piece of ice is burned, about the size of a nut, "drilling" into the ice until almost all has melted. The H2O then shows the reaction of H2O2. Traube (DE 27163) suggested technically preparing H2O2 by burning flames from CO or H2 (or illuminating gas, water gas) against cooled water. The peroxide is usually destroyed by the heat, but water has a cooling effect which partially prevents its decomposition. That would do for an interesting experiment.

If generating a H2 flame from a simple flask using acids and metals, the flask should not be large in volume in proportion to the mixture, so no air can get in and cause an explosion on ignition (the LEL of H2 is 4% air volume, UEL is 75%). The mixture should generate a good flow of H2. I've generated a small flame by putting my finger over the delivery tube opening to build up pressure from the H2 until noticeable, and then release and carefully but quickly ignite it wearing at least a face shield. But, frankly, IMO generating a decent working H2 flame is too much trouble also from the foaming of the acids and explosions (a flashback arrestor could be useful). The patent also says the yield is raised considerably if the burning flames against the water have air lead through them, even better if the flammable gases premixed with air and under pressure are ignited and then ignited and led into the water. I've decided to try it, but using a concentrated MAPP-O2 flame (which burns about as hot as H2-O2) from a small torch.

Some icy snow pieces were put into a glass bowl and these then all mostly melted using the blue oxy-MAPP flame, the flame was also sunk into some of the water so it spreads out onto the surface, and hovered around the surface of the water for a few seconds, all of it melted where after a few seconds the heating stopped. Then after the heating, the melted solution was largely now still cool. 49.3 g of the total liquid now had 0.4 g solid KMnO4 added and there was a small, but visible effervesence, much milder than with the common commercial peroxide. The mass loss equated 0.1 g, which then equates to 0.4% concentration. Another solution made in the similar fashion will turn KI yellow-brown. Heating the solution longer e.g. so it lightly steams seems to largely decompose the H2O2.

Using larger, strong flames from C3H8-air flame gave as expected, unappreciable results. Heating with a large MAPP-air flame a few ice snow pieces until all was melted and the solution became warm: 118.4 g of this liquid gave off about 0.1 g with 0.4 g KMnO4 gave very slight effervesence and foam, weaker than above, about a 0.18% concentration. Although C3H8-air didn't show any results, a small oxy-C3H8 flame does because of the higher temperature. Heating a few ice snow pieces until melted, and the solution cool, already shows a few bubbles at the bottom of the liquid, 76.5 g made by this was a 0.28% concentration. This solution also gave yellow color with KI.

[Edited on 6-9-2008 by Schockwave]

aqua_regia - 6-9-2008 at 02:31

Sorry, is in romaine, from C. D. NENITESCU - CHIMIE GENERALA (C. D. NENITZESCU - General Chemistry)

[Edited on 6-9-2008 by aqua_regia]

Attachment: scan0004.pdf (925kB)
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Panache - 6-9-2008 at 17:14

Quote:
Originally posted by Ritter
Union Carbide produced peracetic acid using 30+% H2O2. The dilute H2O2 from this process was returned to a distillation column where ethyl acetate was added & the H2O2 concentrated by distilling off the water as the ethyl acetate azeotrope.
I was told about an accident they had where the peroxide concentration sensor failed & the column got to the point where it was at least partially filled with 99+% H2O2. The resulting explosion launched that column into the next county.


I figure that was prior to 'fail-safe' becoming common plant vernacular. Is there a process that Union-Carbide didn't have an explosion with, correct me if i am wrong but it was a Union-Carbide NaNO3 storage warehouse in the US that also exploded once, not to mention their track record in India.

As if in australia government legislative hypocrisy was not blatant enough, H2O2 it is available as a 50% solution here, $79.00/5L, stabilised though.

Taoiseach - 8-9-2008 at 08:14

I know there're threads on this already but just wanted to bring this up because nobody seems to have tried this yet:

Washing detergents like Oxyclean contain about 15%w of perborate or up to 20%w of percarbonate. Theoretically about 30 grams of pure H2O2 could be obtained from a kilo - not that bad considering its ass cheap. Neutralization with acetic acid and destillation with minimum amount of water could do the trick. No risk of peracetic acid forming I think because it requires very low pH (industrial production uses conc. H2SO4 and leaves the mixture for several days to obtain a high % of peracetic acid). After neutralization the mixture should be stable nuff for careful heating.

[Edited on 8-9-2008 by Taoiseach]

Taoiseach - 12-9-2008 at 14:13

I should do some calculations before posting shit like my previous post :mad:
Actually its not that easy at all.

I found a washing detergent wich says >25% percarbonate on the labeling. Assuming the rest is sodium carbonate, I did some calculations. Neutralization with 25% acetic acid would give a 3% H2O2 solution at best - worthless :( The problem here is the water content of 25% acetic acid (775g/L). Plus you need to neutralize ALL the carbonate ions in the carbonate AND percarbonate which produces even more water.

Neutralization with HCl might give higher concentrations, but HCl is oxidized by H2O2, forming chlorine.

If one can obtain conc. H2SO4, a ~30% solution of H2O2 should be formed. Thats decent, but then again, if conc H2SO4 is available, so will be conc. H2O2.

The general observation is: No matter which acid is used, you cannot obtain H2O2 in conc.>30% because of the water produced by CO3(2-) neutralization. Unless you find a detergent with more than 25% percarbonate content, that is.

Becised, there will be all sorts of ions floating around in the solution, rendering it worthless for synthesis. Thus vaccum destillation is a must. :(

Picric-A - 13-9-2008 at 08:28

why dont you just by 30% H2O2, it is CHEAP and readily available,
by the time you have found and bought a decent % percarbonate you could of bought the H2O2... no vac. distillation required!

497 - 14-9-2008 at 18:52

I don't know how many times this has been said, for all kinds of chemicals in many threads, but I'll say is again. Some people can not buy concentrated H2O2 (or X other chem) because of location or whatever other reason. Thus saying "Well why don't you buy it???" is totally useless. Obviously we know it is available in some places, we know whether we can get it or not. Maybe if you pointed out some new source that had not been discussed, it might be helpful.

Also with all the supposed liquid explosives plots and such, don't be surprised when anything over 3% becomes heavily regulated or totally unavailable.

Finally, there are many discussions throughout this forum on the synthesis of chemicals that are perfectly available, and yet we want to synthesize them anyway for various reasons. Just because it can be bought doesn't mean it preparation shouldn't be discussed.

[Edited on 14-9-2008 by 497]

symboom - 28-12-2011 at 02:48

hmm vacuum distillation of hydrogen peroxide with phosphoric acid as the stabilizer so i have a vacuum filtering flask some how have a rubber stopper with a hose out the top of the flask that contains H2O2 another vacuum filtering flask with sealed rubber stopper and boil off the water at room temperature.