Chemicals I Have Made – Hydrogen Peroxide

hydrogen peroxide

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.

 

Chemicals I Have Known (and Made) – Hydrogen Cyanide

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As I look back on my career in industry, I realize that I became inured to the chemicals I dealt with and produced. I will be posting occasionally on some of the materials I worked with and made during the first part of my career. The first chemical I worked with was hydrocyanic acid – a simple molecule consisting of a hydrogen atom, a carbon atom, and a nitrogen atom (HCN). This molecule is so simple that there are molecular clouds in space where HCN is found, released from stars that have synthesized carbon and nitrogen in their core. But HCN has a well-known reputation as a poison, one that prevents oxygenated blood from being able to deliver their life-giving load to cells. Once oxygen transport ceases, energy production in a cell stops, and the cell and the organism that contains the cell dies.

 

So at the chemical plant I worked at, one of the requirements to work in the cyanide area was to ensure that I could detect cyanide leaks so I would not wander into an area with a fatal concentration. This was done by means of a sniff test. Three beakers of water were set on a tray. Two were plain water, and the third had a concentration of cyanide in it that resulted in small amounts of cyanide vapor in the air above the beaker. To pass the test, you had to tell which beaker held the cyanide. The first time I took the test, I was guessing somewhat. None of this “bitter almonds” smell, just something that was a little off. By the last time I took the test, almost 10 years later, I picked up the beaker with the cyanide and before it made it halfway to my nose, I put it back down on the tray and said “That’s the one.” What was originally too faint for me to be certain had become so overwhelmingly repugnant over the course of a decade that it gagged me.

 

Cyanide. What’s it good for? Hydrogen cyanide is used in quite a few chemical processes as a feed stock. One of the chemical processes is used to make another chemical called methyl methacrylate (MMA), used in acrylic paints and in plastics like Plexiglass. My chemical plant made MMA as well, but that’s a story for another day. The other main use of cyanide was to make sodium cyanide, which is used in the mining of precious metals. Sodium cyanide solutions are able to leach small concentrations of gold, silver, and other precious metals out of ore, allowing it to be concentrated and extracted into product. Our plant produced sodium cyanide as well as HCN. Some HCN is shipped to other locations for use. When it was shipped, the tank cars that contained it were painted in a distinctive manner. They had red stripes on them – one that circled the car lengthwise, and one that circled the circumference of the car, forming a cross on both sides of the car where the stripes collided. These cars were called candy stripers in the trade.

 

Hydrogen cyanide is produced when ammonia, natural gas, and air are heated and passed over a platinum – rhodium gauze mesh. The off-gases are then absorbed, and the cyanide produced is concentrated and purified. At our plant, HCN was stored in tanks surrounded by dikes. One of our safety features was flare guns mounted on posts throughout the tank farm. If the worst happened, and liquid cyanide were to leak out onto the surface of the dike, folks were instructed to fire a flare gun and set the liquid on fire. HCN is volatile (78ºF boiling point), but the vapor will not explode. Instead, it will undergo a deflagration where the combustion wave front is slower than the speed of sound. Other gases like methane will explode, where the combustion wave front is faster than the speed of sound, which causes the pressure wave that creates damage in an explosion. So for HCN, it is much better to let it burn and eliminate the toxic vapors evaporating from the liquid surface.

 

One day in 1979, I was out at the plant on a Saturday. I remember that Dr. Jenks was there on that day as well, and he invited me into his office. Dr. Jenks was one of those older generation chemists who knew everything about the chemistry and processes. He had a wooden box in his office, about 18″ on the narrow sides, and about 10′ long. In that box was the replacement platinum/ rhodium gauze for the catalyst change. At that time, when precious metal prices were at a 30 year high, his office held about 2 million dollars in platinum and rhodium. I was impressed.

 

My main job in manufacturing support was in the waste treatment process. As you can imagine, the waste water from these cyanide processes needed special treatment and segregation from other waste water. The “state of the art” water collection system consisted of cypress lined trenches, with cypress boards covering the top. This ran downhill to the bottom of the plant, where we had the Trade Waste water treatment facility. Waste water came into a collection point, where sodium hydroxide was added to make sure that the water was basic. If cyanide ions were in an acidic solution, cyanide vapor would be released above the solution, and that is not a good thing. So once the pH was adjusted to make the waste basic, then it would be mixed with liquid chlorine. Our plant produced sodium metal and liquid chlorine, so we had only to send the chlorine down a pipe to the water treatment plant, and mix it in with the waste water. When the chlorine hit the basic water, it produced chlorine bleach solution (sodium hypochlorite). Bleach attacks the cyanide and converts it to a non-toxic degradation product. To ensure that the reaction took place, after treatment the water was diverted into what were called 8-hour ponds. These ponds were on either side of the treatment building, and were unlined ponds where the water was held until the reaction was complete. Then the water was released into a baffled chamber called the one hour pond where it was analyzed to make sure that all of the cyanide was destroyed, and after the last test, the water was combined with the other sewer waste and went into the City of Memphis sewage treatment system. Unfortunately at the time, our interceptor sewer did not hook up to the sewage treatment system, and the water along with all of the domestic wastewater was discharged directly into the Mississippi River. Environmental protection has definitely improved in the 40 years since I was working in this process.

 

I would imagine that the staffing situation for the Trade Waste process has also improved. Back when I worked at the plant, there was a single operator who was stationed at the treatment plant. This individual sat in a central control room, and on either side of the control room were the chlorine injectors with the liquid chlorine flowing through them. Now, I don’t know about you, but I would be hesitant to work by myself, with cyanide-laden waters and liquid chlorine surrounding my office, but back in the late ’70’s, I didn’t think as much about the implications of what could go wrong. The plant had a safety procedure where the person working in a remote location had to check in with the main control room at least once per hour. Believe me, at that time, so much could have gone wrong in an hour’s time that the operator could have been dead for 59 minutes. But it never did at that facility during at least the first 30+ years of operation. Looking now at the facility on Google earth, it is obvious that they have made significant changes and improved the safety of the treatment operation. But some of the facilities look similar to what I worked with 40 years ago.

 

There’s much more I could go into. Cyanide has some amazing chemistry, and the waste treatment is almost an art unto itself. I did some large-scale testing there where we added a hydrogen peroxide waste stream that was what I considered to be fun chemistry. But it was definitely a good process to work on for my first real production support for making a nasty chemical.

Why so close? Chemical plants and oil refineries, and water.

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Chemicals, oil, and water are linked eternally in a faustian bargain. In order to produce most chemicals, and all petroleum products, it is necessary to have access to immense quantities of water. Thus, the infrastructure for these industries is found in the low-lying areas alongside of rivers, and within the inlets and bays along the coastline of the oceans. When the inevitable floods happen, the potential for releases of chemicals and oil, and even explosions as seen in Crosby Texas this week can and will occur.

Why is there this dependence on huge quantities of water? In order to make many chemical reactions occur, it is necessary to provide heat. That heat normally comes in the form of steam. Steam is also used to enable separations of chemicals through distillation. The tall columns seen in chemical plants and refineries are usually distillation towers, where products and wastes are drawn off at various levels in the towers. These products must then be condensed, and they are condensed in heat exchangers with water being used to cause the vapors to condense. The chemicals and the water don’t mix in these condensers, since they are found on opposite sides of the heat exchangers. But immense quantities of water are used in heat exchangers, and the water is thus warmed, reducing its effectiveness in condensing and cooling chemicals.

The water used in heat exchangers and condensers may only be used once. This is single-use water and it is necessary to have a large volume of water nearby in order to release the warmed water without adverse ecological impact. If the water is reused, then it is necessary to cool the water back down in order to use it again. This is done in cooling towers, and you normally will see the plumes of water vapor coming up from these large structures, where water is cooled through evaporation as it drips on down through the wooden framework of a cooling tower. Cooling towers increase the concentration of salts in the water, since a portion of the water is lost to evaporation and may have many cycles through the cooling tower before being discarded to a body of water.

Since it takes lots of energy to move large quantities of water, and lots of money to run long lengths of piping, most chemical plants are found just adjacent to the water. They are sited so that they are above the normal flooding levels, but when unprecedented flooding happens like with Harvey, they are supremely vulnerable to damage from water. In my career in the chemical industry, I worked at two plants (in Tennessee and in West Virginia) that were situated along rivers. The plant in Tennessee did have problems long after I left when flooding from the Mississippi caused backwater flooding that buried part of the plant, which was situated on a smaller feeder stream. Fortunately, it didn’t cause the release of chemicals, and was not a large problem, but it highlights how close proximity to water comes with its own set of risks.

I have been to plants in Texas that were totally inundated from the floods this week. One along the end of the Houston Ship channel, that immense concentration of oil and chemical plants along Texas 225. The other was in Beaumont, situated right next to the marshlands leading to the Gulf of Mexico. The facilities at these plants are designed to be safe and to be able to be shut down without causing chemical releases. But. There are limits to what you can do and still be safe. When you have feet of floodwaters covering a site, then the power of the water can do things that cannot be controlled. Water can erode pipe supports, and the dangling piping will bend and break, releasing the contents of the lines. Floodwaters can shove vehicles and boats into pumps and piping, causing them to break. Even in the normal process of shutting down facilities, excess venting and flaring of flammable and toxic compounds can happen, which can cause irritation and concern among the neighbors of these facilities.

Just as there is a faustian bargain between these facilities and water, there is another relationship that comes into play. That is the relationship between the workers and their families, and their proximity to the plant. Very often the workers for these facilities are found in the neighborhoods surrounding the plants. Entire generations of workers have grown up nearly in the shadow of the towers of refineries and chemical plants. This is especially true in the region around the Houston Ship Channel. The towns of La Porte, Pasadena, Deer Park, and Baytown have a symbiotic relationship with their industrial behemoths. Only a single road separates the residential areas from the properties of the oil and chemical companies. Quite literally, the companies and the towns are all in the same boat at times like now.

The plant that had the explosions this week was a different type of chemical plant. This plant was not adjacent to a large body of water. What it manufactured was a chemical that is essential in the manufacture of plastics, but by its own nature, it was extremely unstable. In my chemical plant in West Virginia, we also manufactured a similar material. These materials are known as polymerization initiators, and they make it possible for chemicals like ethylene (two carbons bound by double bonds) to react with each other, and form long chains that we know as plastics (polyethylene). The materials we produced in West Virginia also have to be kept refrigerated or they will grow unstable and catch fire. Part of the lore of the plant involved the time when the manufacturing line for this material had a problem, and the temperature rose to the point where the chemical decomposed and ignited. That fire was remembered long after everyone who worked during the fire had left the plant. What made the situation in Texas worse, was that the organic peroxides they made are not only flammable but are explosive when they decompose.

Part of the manufacturing process for chemical plants involves process hazards reviews. In these reviews, the participants go through a systematic review of the inherent hazards of the process and facilities, and determine if there were adequate safeguards to prevent incidents and injuries. Sometimes a significant hazard is discovered, one that had not been previously considered, and then the management of the plant faces the task of getting the fix done to remove the hazard. Since it takes time to implement new facilities (and get the authorization to spend the money to build facilities), normally there are administrative controls that are put in place to temporarily mitigate the risks. But even though I participated in many process hazards reviews in my career, I do not remember ever having considered the case of having my plant submerged in multiple feet of floodwater, and having no way to get anything working for days at a time. I imagine that the chemical and refining industries will have to go through substantial work trying to come up with new safeguards that will prevent releases and explosions such as are being seen in Texas now.