[Govyn]

Hi everybody,

I have a large quantity of expired cumyl hydroperoxide stored in an explosion proof bunker. I've had environmental waste disposal companies quote me extremely high prices for the disposal of this stuff. I was wondering if there was an alternative of disposal. Could we neutralize it in house safely and possibly cheaper than the disposal companies.

I'm not against paying for proper disposal, but I would like to make sure that I'm paying for a service that I can't do myself.

I await your feedback

Thank you and have a good day

[discodermolide]

You could try adding it to a well stirred aqueous solution of sodium bisulfite with cooling. You should get Cumene-OH and sodium sulfate.

[Doc Oc]

My apologies if I'm telling you something you already know, but I believe one of the biggest dangers with peroxides is that they form shock sensitive crystals around the threads of the cap so if you try to open the bottle it will detonate.  If you can see crystalline buildup on or around the cap I wouldn't mess with it.

[Govyn]

Hi J-bone, I am aware of the danger concerning the crystals but thank you for your concern. Last time I check on the containers there was no build up...most of them have not been opened yet, they still have a film glued on the bottle under the cap.

Hi discodermolide, I found some good info about sodium bisulfite and sodium sulfate but I can't seem to find much about Cumene-OH. Compared to it's original form, is it safe to handle and to dispose of?

Thank you both for your quick responses.

[408]

Cumene hydroperoxide is a liquid.  Crystals in the cap are not a big issue.    This is not TATP in terms of handling issues 

In terms of organic peroxides, this one is pretty tame.  If it was not, you could not buy it from aldrich.    It is said to be insensitive to shock.

Reduction to the alcohol with zinc or something would be easy, then dispose of as normal organic waste.  Or dissolve in acetone or some flammable solvent and burn it.


Or wait for me to start my own explosive waste disposal company, I will undercut the other guys by half.

[Govyn]

Hi 408, thanks for the additional info...How do I know when the reduction process is complete? Is there an indicator I should use or will there be clear signs that the reaction has run it's course.

Thanks again everybody

[408]

You buy organic peroxide indicator paper to test that.



So you will not wait for me to start my own disposal company then 

[Govyn]

Hi 408,

It depends, what's your time frame to get it up and running?

btw I have about 350 kg to dispose of.

[Doc Oc]

For what it's worth, ether and THF are capable of forming the crystals I was talking about, but I don't know enough about this particular peroxide to comment.  I also don't know how things change if the bottles are unopened.

The paper 408 is talking about is starch iodide, it turns purple in the presence of peroxides.

[408]

Several years    It was more of a tongue-in-cheek comment.

[orgopete]

btw I have about 350 kg to dispose of.

I would consider treating it with acid. That is the commercial process for the production of phenol and acetone. I don't know the particulars of that reaction, how exothermic, etc. Since you have such a large amount, I would become tired of running 3,500 x 100 g batches in any process. A 350 kg x 1 batch could create so much heat that could not be controlled because of the limited amount of surface area so it too could be dangerous. If you have 350 kg, could you sell it to someone interested in the peroxide or to someone basic in the phenol-acetone process?

[discodermolide]

btw I have about 350 kg to dispose of.

I would consider treating it with acid. That is the commercial process for the production of phenol and acetone. I don't know the particulars of that reaction, how exothermic, etc. Since you have such a large amount, I would become tired of running 3,500 x 100 g batches in any process. A 350 kg x 1 batch could create so much heat that could not be controlled because of the limited amount of surface area so it too could be dangerous. If you have 350 kg, could you sell it to someone interested in the peroxide or to someone basic in the phenol-acetone process?

Crap, if you do the treatment in a large enough vessel, say 1000-1600L you will have no problem with heat exchange if you are in a proper pilot plant anyway the reaction will be addition controlled, so heat removal should be no problem. You place 10-20% aqueous solution of sodium sulfite in the reactor, cool to 10°C, add dropwise keeping the temp between 10°C and 20°C a solution of the hydroperoxide in toluene, stir well.
You can also do it at the reflux temperature of the solvent mixture, reflux cooling, providing you control your solvent loss by evapoartion.
I am a development chemist so I am aware of these things. What is essential is to to all the thermal analysis (DSC etc) before you start so you know what to expect.
I've done things like this on a much larger scale then 350kg, just know your system before you start

[Govyn]

Well, we manufacture fiberglass tanks and piping, so we're not equipped with the instrumentation to do the precise temperature control you mentioned.

However, I was wondering if this could work...

Could we pour the peroxide in a large but shallow dish, 12 ft across by ~18 in deep and periodically add small amounts sodium bisulfite for example. The dish would be left outdoors in our storage yard.

Although there is no temperature control, I'm hoping the large surface area might dissipate enough heat.

What do you think?

Govyn

[discodermolide]

I would do it the other way around. Put your sodium sulfite in the dish and add the hydroperoxide. That way you avoid any adiabatic temperature increase leading to problems.
Monitor the temperature if you can and stir well, if you can.
You could also treat the hydroperoxide with base. For example,  Hydrogen peroxide + sodium hydroxide gives oxygen and water.

Why don't you put it in one of your fibreglass tanks and surround it with piping and pump cold water through the pipes?
Why did you require the hydroperoxide for this activity?

[Govyn]

The hydroperoxide acts as a catalyst when used with a vinyl-ester resin promoted with cobalt. The problem is too much peroxide was purchased and now it's expired...the curing takes too long and we can't get the mechanical properties we need. Another problem is that although the peroxide is expired, it still very reactive.

I have found a hazardous waste disposal company that could dispose of it for us but the price is absurd, that's why I'm looking for an in house method. I'll present the two alternative to the VP and we'll see where we go from there. Even if the in house method turns out to be cheaper the safety aspect is climbing quite rapidly.

Thanks again everybody for all your advice.

If any of you have more suggestions, I'm always open. And if you'd like more info about our processes, ask away I'll do my best to answer.

Wish you all a good day