Chemicals I Have Known (and Made) - Hydrogen Peroxide

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It’s such a cute, cuddly chemical. Found in its brown plastic container in medicine cabinets across the world, it is poured on cuts and scrapes where it foams up in bubbles. Safe enough to be used as a mouth rinse. Good old 3% hydrogen peroxide! But let me assure you, what is safe at 3% strength, is not safe at 35% concentration. Or at 70% strength. Hydrogen peroxide, or H202 , is a chemical that must be given a great deal of respect. In my career, I worked in a process that made H202 for several years, and I’ve seen examples of its power.

 

When tank cars were loaded with H202, the hoses would still contain some of the liquid in the lines. There was an attitude that since this was not an organic material, and since the decomposition products were water and oxygen, it was not worthwhile to ensure that the last drops were purged out of the line. So a metal box was filled with steel scraps, metal shavings, and other pieces of metal with a high surface area. This box was used to decompose the peroxide before it ran into our cypress-lined trench system. On one occasion, significantly more peroxide ran down into the box than was intended, and not all of the peroxide decomposed before it entered the tar-covered cypress trench. Decomposition continued, and the heat released along with the enriched oxygen environment inside the trench, actually caused the trench to begin smoldering. The fire alarm was sounded, and the investigation showed that the fire was essentially caused – by water. That is the power inherent in industrial strength H202.

 

Before I worked at the plant, they had a specialized still that concentrated peroxide to 90% purity. That strength was used as a rocket fuel, and as a propellant for torpedoes. I never heard of any stories about accidents with that grade, but it would take very little in order to release the energy found in that strong of a chemical. After I left the Memphis Plant, I heard about something that happened to a tank car outside of the plant. Tank cars for peroxide were made of about 1/2″ thick aluminum. One night, a tank car essentially exploded, opening up the top like a pop can. The thought is that someone playing with a rifle, shot the tank car. There is a little organic material that sits atop commercial grade H202, which reacted to form organic peroxides. The energy from a rifle shot caused the organic peroxide to detonate, which triggered the release of the oxygen from the decomposing peroxide. I saw the car on a trip back to the plant. It clearly showed that there is a lot of energy available with 70% H202. I have searched diligently on the internet but I can find no on-line evidence of this incident.  One can only imagine what would have happened if this incident occurred after 9/11.

 

The process for making H202 is complex. An organic solution called working solution is the key to creating the H202 molecule, which then recycles to begin the process again. The working solution first enters the hydrogenators, where hydrogen gas contacts a catalyst of palladium chloride coated out as palladium metal on alumina particles. The palladium chloride comes in a solution form in 5 gallon pails, costing multiple thousands of dollars per pail. After the catalyst is filtered out, the working solution goes into the oxidizers, where air is blown through the solution. Hydrogen grabs onto the oxygen, and forms H202, which then is extracted with water, and concentrated in distillation stills. The working solution then returns and is ready to run through the loop once more.

 

That is a highly simplified version of the process. In practice, there is art involved. The active chemicals in the working solution can degrade over time. Therefore it is necessary to divert a side stream of working solution to flow through alumina, where the impurities that form in the hydrogenation step absorb onto the alumina. The whole process with the catalyst and the hydrogenation step is labor intensive, and it is always necessary to withdraw a portion of the catalyst and replace with fresh catalyst. To prevent that expense, and to achieve higher yield, the plant I worked at had invested in what is called a fixed bed hydrogenation system. This had shown impressive results in lab-scale testing, and in pilot plant testing, where 5-gallon sized vessels were used to prove the effectiveness before you built a 1000-gallon facility for commercial production. The new commercial facility was commissioned, and put in service.

 

But problems developed very rapidly. Even though the pilot plant testing did not show it, the commercial scale facility developed some hot spots inside the hydrogenator. This caused the active compound in the working solution to degrade much more rapidly than inside of the fluid bed hydrogenators. Since the investment in the working solution was several million dollars, it became imperative to find some way to reverse the damage. Lab work was expedited, and a solution was identified. They needed some engineer to manage the project and get the equipment ordered, installed, and functioning. I was plucked from the cyanide unit(see  Chemicals I have made – Hydrogen Cyanide ) and put in charge of the project.

 

It was a true baptism into project management. I got to travel to see the vessel that we were buying in the fabrication shop, up in the extreme northwest corner of New Jersey. There you were more likely to see a black bear than to see a Joisey girl. But the best part of the project was that I got to install and program a Programmable Logic Controller (PLC). Now this was back in 1980, and these were brand new toys  tools that used all of the advances in semi-conductors that were available. You could replace a whole rack of single-function logic switches, with a single unit that could do nearly unlimited functions. I had a lot of fun learning the ladder logic that went with this, and getting the system to work as intended. We started up our treatment unit – and it didn’t solve the problem. The working solution was still getting degraded, even when the fixed bed unit was operated at only a fraction of its intended production rate. The equipment I installed was abandoned, and the large fixed bed unit was shut down and eventually dismantled. But I had learned valuable skills and had managed a significant project by myself.

 

The manufacture of H202 is not different by chemical manufacturers. At the time I worked to make H202, all manufacturers used the process I described. Eventually, the unit I worked at was sold to another company in exchange for one of the other companies processes. I left H202 when I got a promotion to be a process supervisor for the manufacture of acrylonitrile. But that’s another story for another time.

 

Published first on my blog at https://evenabrokenclock.blog

Comments

wsucram15 Added May 14, 2018 - 12:59am
You know..one of the best cleaners is hydrogen peroxide. I keep it in a hospital formulation at my house all the time.  Its expensive and cleans like bleach but in some cases better w/o the smell.
Still love my beach..but my isnt in a brown cuddly bottle except for the stuff you use to clean cuts.
Did you know the brown bottle stuff takes blood stains out? Its the only thing I have ever found that removed blood or any other organic stain. Bubbles it right out of the carpet. But you have to use a clean white rag and dab it out.  
You also cant leave it sit..its a hands on type thing. But it works..great cleaner. Great antiseptic and its cheap.
Jeff Jackson Added May 14, 2018 - 4:16am
Interesting article Even. Is it true that 100% H2O2 burns on contact with air, which was why it was used as a rocket fuel?
Even A Broken Clock Added May 14, 2018 - 9:37am
Jeannie, the 3% solution in the brown bottle does take out blood, and I imagine wine stains as well. It is similar to what oxyclean does, which is a peroxide bound up with other ingredients. The plant where I worked had a process where peroxide was reacted with a boron compound to make sodium perborate. That's similar to oxyclean, but don't know if that is the active ingredient.
Even A Broken Clock Added May 14, 2018 - 9:42am
Jeff, I don't know if it is possible to concentrate up to 100% peroxide. The 90% limit is the highest that I've seen as a commercial grade. And that strong of peroxide would not actually burn, but any organic material that it came into contact would ignite, since the decomposition would release oxygen, and the heat of the decomposition would raise the temperature of the organics to its autooxidation temperature.
 
The use of peroxide for rocket fuel involved combining H2O2 with hydrazine, or N2H2. There's a technical term called specific impulse that is important for chemical rocket fuels. This combination of chemicals has one of the highest specific impulses available. Unfortunately, hydrazine is toxic, and so it tends to be used as an attitude adjuster for satellites instead of as a main booster anymore. The whole field of rocket propulsion and the chemicals used to move things against earth's gravity is a fascinating one as well.
Ari Silverstein Added May 14, 2018 - 11:04am
Is there some kind of point you’re trying to get across in writing this article? My takeaway was that chemicals can be very dangerous.  Or were you trying to say something more profound?
 
One brief question that will probably demonstrate my ignorance about chemistry than anything else: Is Hydrogen Peroxide H2O2 or is Hydrogen Peroxide 3% H2O2 and 97% ______?
Dino Manalis Added May 14, 2018 - 12:20pm
 Chemicals can be useful, but they can also be deadly, that's why the FDA has to constantly evaluate chemicals to determine long-term effects.
wsucram15 Added May 14, 2018 - 12:37pm
I use the brown bottle and no its not like oxy clean, which is a brightener.  Nothing takes blood out of carpet, this removes even set in stains.  Good stuff.
Now the other stuff I use is much stronger and NOT in a brown bottle, it acts like a bleach almost. 
Ive never seen anything like it but works well.  If its a good chemical I will use it to clean.
wsucram15 Added May 14, 2018 - 12:44pm
I should not say that about oxy clean..I just dont like the product. Its never cleaned very well for me.
Even A Broken Clock Added May 14, 2018 - 12:55pm
Ari - I'm writing a series of these posts about the chemical processes I worked on during my first decade of my career. I look back and I realize that there were some really crazy things I was involved in, and if I hadn't been grounded in chemistry, I'd probably have been scared out of my wits.
 
You know how local news says if it bleeds, it leads? Well since I'm limiting my post length, I figure there will be more interest if I write about some of the more dangerous parts of the job. My first post in this series was on hydrogen cyanide, so you can't get much more dangerous than that.
 
I like to try to teach a little bit, and hopefully I'm writing in such a way that folks who don't have a science background can still follow the post.
 
As for your question, a molecule of hydrogen peroxide is indeed H2O2. That molecule is contained in a water solution. So if you see 3% H202, the rest is 97% water. 35% H202 = 65% water. Hope that helps.
Even A Broken Clock Added May 14, 2018 - 12:58pm
Dino - the FDA regulates drugs, it's the EPA who has a system to keep track of new and unexpected reactions of chemicals. But those with known risks are already taken into account.
 
Speaking of the FDA, when I dug around in the files, I found the Kosher certification from a Rabbi. Since H202 is used for food bleaching, it was found that we had a Kosher plant. I wondered if we had used boar bristles on the brushes for sweeping the floor, would we have received our Kosher certification?
Even A Broken Clock Added May 14, 2018 - 12:59pm
Jeanne - we've always had good luck with the Oxyclean, especially in the spray bottle for stains. I've seen it take blood stains out. Oxyclean does have other cleaners and surfactants in it as well. But as it's name indicates, it is oxygen bleaching (H2O2) that is the active bleaching agent.
Dave Volek Added May 14, 2018 - 4:21pm
EABC
Nice article. It's always good to learn a few new things. Keep it up!
James Travil Added May 14, 2018 - 7:10pm
Informative and educational article. I always use Hydrogen Peroxide to clean with as opposed to bleach. It is a better cleaner, doesn't stink like bleach, and isn't a carcinogenic like bleach is. Lysol makes a 6% H2O2 cleaning spray with citris that smells and even tastes great, lol! Fun fact, the standard household brown bottle is brown to keep the sunlight away from peroxide (which breaks it down faster).
A. Jones Added May 14, 2018 - 7:11pm
Some physicians claim that infusing H2O2 (3%) into a patient's blood can be therapeutic for a number of diseases and ailments. Here's one random link of many:
 
https://www.drceaser.com/therapies/intravenous-hydrogen-peroxide-therapy
 
Also, at many health food stores, food-grade H2O2 of 12% or more is available. The idea is to add a small amount (1/4 teaspoon) into a quart of distilled water and to drink a glass of it at regular intervals. Have no idea if it helps people or not.
wsucram15 Added May 15, 2018 - 2:52am
EABC..I guess Im not a off the rack type gal.  I like commercial cleaners (i used to work for a chemical distributor) and I use outstanding products in my home.   Oxy clean is good for a laundry additive, but I actually like tide stain remover better or even spray and wash.   I use borax as an additive.
 
The one I am talking about in commercial grade form, you have to special order is one of my favs.  Cleans like bleach, without the stain. I checked all of that is less than 4-5% hydrogen peroxide.   You can clean with 98% but it kills plant life, etc.   Plus I think anything stronger than what 6-7%, is no longer able to be around vegetation or food, not sure on that one.  But  some people use the 98% with citric acid to clean various substances. 
 
As far as helping people, sulfer (food grade or in products) is good for your skin.
 
Also diatomaceous earth (food grade ) is amazing for both people and pets.  It does so much I cant even list it all here both internally and externally.
 
Even A Broken Clock Added May 15, 2018 - 10:00am
A. Jones - I wasn't aware that you could buy that strong of a solution over the counter. I'd be very wary about infusing peroxide of any concentration into the blood. I tried to look at your link but it came up with some sort of promotion that my protective software wouldn't allow a link through.
 
One thing that you do need to watch out for with any peroxide is to avoid getting it in the eyes. We were told of the horrible effects of peroxide in the eyes, and of course for us in the plant, the entire area was a goggle area. 12% is more risky than 3%, but your normal 3% is not certified as food grade, so I can understand the use.
Even A Broken Clock Added May 15, 2018 - 10:02am
Jeanne - Thanks for the additional information. Diatomaceous earth is used a lot in chemical manufacturing for filtration as well. Those little critters did a good job building up their cell structures.
Even A Broken Clock Added May 15, 2018 - 10:27am
James - I wasn't aware of the Lysol peroxide product. I'll have to look for it. Incidentally, it is not the hypochlorite (chlorine bleach) that is carcinogenic, but it is the potential for some of the compounds that are oxidized by chlorine to be carcinogenic. For example, in the water supply, materials that contain nitrogen and are partially oxidized by chlorine form chloramines, which may be carcinogenic. Other examples exist.
A. Jones Added May 15, 2018 - 6:30pm
http://educate-yourself.org/hp/hydrogenperoxidephysiciansIOMAlist2002.shtml
 
"U.S. & International Physicians Who Offer IV Hydrogen Peroxide & Bioluminescence Therapy"
 
"The 2002 Physicians List from the International Oxidative Medicine Association (IOMA) is published in Hydrogen Peroxide, Medical Miracle  by Dr. William Campbell Douglass, MD (2003 edition) . I will update the list when I receive the 2006 list from IOMA. Undoubtedly more physicians and more states will be listed in the 2006 list. If you are a physician (or if you know of a physician) who offers IV hydrogen peroxide infusions or Bioluminescence therapies and you are not affiliated with IOMA, please send me the names and I can list those physicians on a separate, unaffiliated list."
 
"International Oxidative Medicine Association (IOMA)
 
The International Oxidative Medicine Association (lOMA) was established by Charles Farr, MD, PhD, to train and assist qualified physicians in giving hydrogen peroxide therapy. IOMA is a 50lc not-for-profit education and research foundation. The Foundation has a continuing education program for physicians to keep them current on the latest findings in oxidative medicine. Specific medical information or recommendations are not available through the Foundation and must be provided by your personal physician. Address any correspondence to:
 
I.O.M.A.
P.O. Box 809010,
Oklahoma City, OK 73189
 
Updated copies of the following list are available from IOMA upon receipt of a written request and a $5 donation"
***
IV Hydrogen Peroxide Therapy
https://www.youtube.com/watch?v=WH4p_NA9seo
Even A Broken Clock Added May 15, 2018 - 7:15pm
A. Jones - thanks for the links. I understand the thought behind the use of peroxide via IV, but the claims made that it boosts the immune system by selectively attacking viruses and bacteria seem excessive at best. What you have is a non-specific oxidizer that will be an equal-opportunity oxidizer and try to react with whatever it finds in the bloodstream. Since hemoglobin contains iron, and peroxide tends to like metal ions for decomposition, I would expect if any selective oxidation were to occur, it would be with red blood cells. But I am not a biochemist, so I can't say for sure.
Leroy Added May 16, 2018 - 5:55pm
Thanks for the interesting article, Clock.  I enjoyed reading it and look forward to future editions.
Tubularsock Added May 17, 2018 - 11:55am
Broken Clock, a very interesting article.
 
Tubularsock really hasn’t given Hydrogen Peroxide much thought.
 
Have used it as a disinfectant for cuts with amazing results but haven’t branched out into propelling Tubularsock’s torpedoes as of yet.
Michael B. Added May 17, 2018 - 10:54pm
Nice post EABC, and a refreshing change! Yes indeed, H2O2 is no joke. Several years ago, I was using a 30% concentration as part of a chemical compatibility test and got a few droplets of it on my right hand, which instantly resulted in searing pain and severe discolorations where it made contact with my skin.
 
I think that was another "secret weapon" of sorts, as German scientists found ways to make 90% concentrations of H2O2, which they used in their rocketry during WW2. The Jet Pack of James Bond fame is essentially a H2O2 rocket.
Flying Junior Added May 18, 2018 - 4:29am
February of 2006, I was lucky enough to purchase and adopt two extremely beautiful dark red Golden Retriever male pups.  The one I named William was the pick of the litter.  Mrs. Junior chose, (or maybe the pup chose her,) his little sparring partner whom she named, Chauncey. 
 
We had done some research into the breed being keenly interested in Retrievers for many years.  There was some risk of cancer and a very common risk of skin allergies, namely moist eczema, aka hot spots.  I had some experience with hot spots with my Retriever and Black Labrador mix, a handsome throwback to the ancient Black Collies of Scotland.
 
The cancer thing proved to be true.  A fellow dog fancier that had bought two quite similar pups in 2006 had trained Sammy and Barley to be agility dogs.  She was devastated when Sammy got cancer when he was only four years old.  She had trained the pair and entered them in several competitions.
 
My Billy got a sinus cancer early this year.  We had to put him down in March.  He was always the healthiest of the two pups.  He was ten pounds heavier.  He was the dominant alpha male.  His coat was fuller, glossier and less prone to hot spots than his lifelong buddy, Chauncey.  But he was the first dog to get a terminal illness.
 
So, I became something of an expert on Golden Retriever hot spots.  I figured it was a small price to pay for such wonderful companions.  I learned to trim back the fur.  In extreme cases, I would always debride the sores with H2O2.  However, I always diluted it fifty-fifty.  One vet said that it was too harsh and burning.  But I still use it in extreme outbreaks on Chauncey.
 
There are other veterinary sprays and even antibiotics that are sometimes required.  But H2O2 is invaluable in debriding the sores, sometimes just to clean the fur enough to make the wounds sanitary to cut the fur back and dry out enough to heal.
 
Chauncey is exactly twelve and one half years old today.  He still has a good appetite and drinks lots of water and loves play.
Mike Haluska Added May 20, 2018 - 1:13pm
The introduction of Chlorine into the drinking water supply has saved more lives and prevented more illness than any other thing in human history (a Civil Engineering application).  Chlorine was also used as a deadly gas during WWI.
Even A Broken Clock Added May 20, 2018 - 9:09pm
To all - I was locked out (as most of us were) from last Tuesday to today. So I haven't been able to reply to any posts. Leroy and Tube - look forward to a post in a couple of months on acrylonitrile, which was the next chemical I worked on.
 
Michael - if you expose 90% H2O2 to a silver nitrate metallic gauze, you will create enough thrust to power a jetpack, or a torpedo. It is extremely powerful stuff. Glad that the 30% didn't cause too much damage.
 
FJ - very interesting about the effect with dogs. I assume that you are diluting the 3% H202 solution, is that correct? Good to hear about your dog's extended life.
 
Mike - You are exactly right. The trade-off of a slight risk for cancer due to chlorinated byproducts vs. dying of cholera or a plethora of other water-borne diseases is well worth the risk. Since we have seemingly adopted a zero-risk tolerance for all things chemical, we have folks calling for the end of chlorination. Well, ozone works well to disinfect water at the source, but then there is zero residual left in the water to deal with any downstream problems. Chlorine retains disinfecting power after the water leaves the treatment plant, and that makes it worthwhile in my mind.
Flying Junior Added May 21, 2018 - 4:12am
Yes