The Dangers of Hydrogen-Based Experimental Fuels

BY RICHARD STILP AND ARMANDO BEVELACQUA

On September 26, 2013, a loud explosion occurred in downtown Orlando, Florida. The explosion shook several high-rises in the downtown area and rocked the Orlando fire station several blocks away. The fire department responded to an unmarked warehouse on the corner of the railroad and Jefferson Street, just two blocks away. On arrival, firefighters saw no signs of fire, but they noted a large cloud of smoky dust behind the building. The inside of the building was also filled with a large amount of dust in the air, and there was evidence of an explosion in that light fixtures were dangling by their wires and drop ceilings were strewed across the floor. Insulation was lying everywhere.

While members evaluated the building, they noted a large hole approximately 50 feet wide by 20 feet high on the north side (rear/side C) of the building. All of the windows on the north side were broken, and terra-cotta tile block was spread over a 100-foot area around the rear of the building. Further investigation found a size “K” high-pressure cylinder that had obviously exploded and was lying almost flat against a wooden floor that was pushed down about 12 inches from the original grade.

(1) This photo was taken from side C of the building. The rear wall was mostly destroyed from the blast pressure. [Photos by the Orlando (FL) Fire Department Arson Bomb Unit.]
(1) This photo was taken from side C of the building. The rear wall was mostly destroyed from the blast pressure. [Photos by the Orlando (FL) Fire Department Arson Bomb Unit.]

The roof over the blast area was constructed of heavy timber and was lifted and dislocated from its mounting points. In the building was some type of electrochemical generator attached to a low-pressure compressor [150 pounds per square inch (psi)] that was further plumbed into a self-contained underwater breathing apparatus (SCUBA) compressor capable of more than 2,000 psi. Several other, unharmed “K” cylinders were in the same room.

The widespread effects from the explosion were evidenced by insulation hanging from the ceiling throughout the building and every light fixture, drop ceiling tile, and temporary wall having been blown to pieces. Despite all of this physical damage, there was no evidence of fire. This was a sudden pressure release from a high-pressure cylinder and not a fire-related explosion. A “K” cylinder at a pressure of 2,000 psi contains approximately 200 cubic feet of gas. The sudden failure of the cylinder caused a shock wave that propagated throughout the building. This shock wave applied a force of just over 2 psi against the entire exterior wall section with enough impulse energy to shatter the wall into pieces and propel debris across the back lot.

Once the fire department completed its initial investigation and the building department evaluated the integrity of the building, it was returned to the owner. The building structural supports did not succumb to the damage. Instead, the damage to the area was not enough to condemn the building, and it was determined that the building was safe for inhabitants. The owner, a self-proclaimed inventor, who had a great deal of success in the past by inventing entertainment props and kids’ games, was now working on a new invention-the manufacture of a flammable gas that could be used to propel vehicles, cook food, and possibly be a new replacement gas for fossil fuel. Naming the fuel “carbo-hydrillium” or just “hydrillium” for short, he was anxious to perfect the process so it can become available as a replacement for propane, natural gas, and even acetylene.

The objective of this article is to provide fire service and emergency response personnel with an overview of hydrogen-based fuels, their related hazards, and the risks they can pose when involved in emergency situations.

(2) Evidence of the explosion was found throughout the warehouse as wires, light fixtures, and insulation were hanging from the ceiling or strewed all over the floor.
(2) Evidence of the explosion was found throughout the warehouse as wires, light fixtures, and insulation were hanging from the ceiling or strewed all over the floor.

HYDROGEN-BASED FUELS BASICS

With the increasing cost of fossil fuels, home grown inventors located in garages, basements, warehouses, and backyard sheds are working to create the next best replacement for traditional hydrocarbon fuels. The inventors are normally good people with good intentions, but many of the processes they use can be dangerous and deadly.

The Internet is full of videos demonstrating how to make hydrogen-based fuel. Some suggest that you install an electrolytic hydrogen generator using water on your vehicle and feed the gas produced into the air-intake system. This process of electrolysis (see “Electrolysis”) makes oxygen as well as hydrogen. These videos suggest that a vehicle using this process will be more efficient and have better gas mileage. Hydrogen is extremely flammable; when combined with oxygen, it is an explosive mixture and cannot be safely stored in compressed cylinders. Furthermore, the gases under pressure may be unpredictable when introduced under the hood of a vehicle or into home-heating systems. The results can be extremely dangerous and can harm the public, including emergency responders.

Hydrillium

(3) The hydrillium generator used the electrical arc of an arc welded to an electrode held in close proximity and underwater to generate the gas.
(3) The hydrillium generator used the electrical arc of an arc welded to an electrode held in close proximity and underwater to generate the gas.

Hydrillium is a mixture of carbon monoxide and hydrogen. It is formed by creating an electrical arc under water, resulting in a gas that contains primarily hydrogen, carbon monoxide, and carbon dioxide. To generate flame, oxygen must be added to the mixture. An open-source search of newspapers shows several significant explosions that have occurred during the production of hydrillium-type gases. For example, in May 2001, an explosion with a fuel known as “Aqua Fuel” occurred in Largo, Florida. The explosion took place when no one was present in the building. Rather than attributing the incident to the product, the manufacturer claimed that a faulty storage tank-a 100-pound, high-pressure cylinder- was the cause of the explosion. According to the St. Petersburg Times, the explosion blew out windows in six houses and rattled neighbors’ nerves.

In the Orlando incident mentioned at the beginning of this article, the inventor used the principle of creating an underwater arc and invented a way to perfect the process he hoped would eventually allow the production of hydrillium on a larger scale. The generator he built automated several processes that previously had been manually controlled. As the gas is generated, it is collected in a bladder bag that feeds a low-pressure compressor. The low-pressure tank, in turn, feeds a high-pressure compressor, where the gas is eventually compressed into a 2,000-psi, “K” cylinder.

The Orlando inventor had his gas analyzed and found that he was producing a flammable gas containing approximately 60 percent hydrogen, 35 percent carbon monoxide, 1 percent-2 percent carbon dioxide, and small amounts of trace gases and water. The flammable range of this gas mixture in air was approximately 7.6 percent to 63.4 percent, an extremely wide flammable range!

After he experienced the explosion that severely damaged his building, the inventor reported that he had had several issues over the past couple of years while producing hydrillium. First, several leaks occurred around the pressure relief device on the cylinder valve where the lead/zinc fusible plug began to leak. Although this might have been the first sign of an issue, he believed at the time that this was caused by a faulty cylinder. Actually, he returned the cylinders to the gas company from which he had purchased them. The company agreed that it was probably a malfunctioning bottle.

The second event took place in his motor home. Typically, motor homes are built with carbon monoxide (CO) detectors because of the possibility of infusion of exhaust gases. During one of his trips when he was carrying a cylinder of hydrillium to use as a cooking fuel, his CO detector activated. He investigated and found that the hydrillium cylinder was leaking from a hole in the sidewall of the tank shell. Again, this event was dismissed as a faulty cylinder. Looking back, it is now easy to see that these were signs of tank failure related to the incompatibility of the gas mixture to the tank.

So, what caused the large explosion on September 26, 2013? The inventor’s issues began when he started to place this gas mixture containing water vapor into high-pressure carbon steel cylinders. Several chemical reactions began to occur; they eventually led to the cylinder’s catastrophic failure.

Incompatibility

Hydrillium contains high concentrations of CO in the presence of both CO2 and water. The Compressed Gas Association (CGA) recognizes that this chemical mixture is incompatible with steel cylinders. The CGA has produced a detailed study, Avoidance of Failure of Carbon Monoxide and of Carbon Monoxide/Carbon Dioxide Mixture Cylinders (CGA P-57-2013, Second Edition). The CGA document states, “Low-alloy carbon steels [steel that has a low percentage of chromium, molybdenum, manganese, nickel, as examples] are sensitive to cracking in a carbon dioxide-carbon monoxide-water environment.”

The stress mechanism is thought to be the local dissolution of iron because of carbonic acid being formed between water and CO2, with general corrosion being inhibited by CO. This chemical process leads to transgranular cracks with branching in the steel walls, also known as “CO stress corrosion cracking.” Over time, the cylinder fails. This failure can be in the form of a leak, as shown by the owner’s previous experience, or can be a catastrophic failure in the form of a pressure explosion as seen in the Orlando incident. [See “Causes of Stress Corrosion Cracking (SCC)”].

OTHER INCIDENTS INVOLVING CARBON STEEL MIXED WITH HYDROGEN

Sandia National Laboratories provides additional documentation on the incompatibility of carbon steel with hydrogen in the position paper Technical Reference on Hydrogen Compatibility of Materials, Plain Carbon Ferric Steels: C-Mn Alloys (code 1100). This technical reference states: “Hydrogen gas degrades the tensile ductility of carbon steels, particularly in the presence of stress concentrations. Additionally, hydrogen gas lowers fracture toughness, and certain metallurgical conditions can render the steels susceptible to crack extension under static loading. Hydrogen gas also accelerates fatigue crack growth ….” This stress process is known as “hydrogen embrittlement.”

While conducting open source research on the production of hydrogen-based “green gas,” we identified a number of other incidents similar to the Orlando explosion. Many of these incidents had tragic outcomes. The findings of our research are as follows:

• On June 13, 2013, in Kendall, Washington, a man was seriously burned when he was attempting to compress a hydrogen/oxygen mixture into a 20-pound propane cylinder. He intended to use this as fuel for his automobile. The individual had been producing the gas mixture through a simple electrolysis process in his garage. The explosion caused shock waves felt throughout the residential neighborhood and resulted in the victim being airlifted to a trauma hospital. The Federal Bureau of Investigation (FBI) and the Bureau of Alcohol, Tobacco, Firearms and Explosives investigated the explosion. The victim was not charged with any crime and never faced criminal charges.

• On January 10, 2011, in Whittier, California, an explosion of an unidentified high-pressure cylinder severed a man’s leg and injured a second person. The explosion blew off the garage door of a residential home. The two men were conducting a similar type of experiment at 2:40 a.m. when something went wrong and an explosion ensued. Both victims were taken to the local trauma center for care.

• Probably the most dramatic incident that has occurred regarding “green gas” technology took place in Los Angeles, California. A number of companies, all owned by the same individual, were making a mixture of hydrogen and oxygen through electrolysis. The companies went by names such as BGX Technologies, Rainbow of Hope Technologies, and Realm Industries before transitioning to the most recent company-Sylmar. The owner of the company lost his first son in an explosion that took place on June 17, 2010. On August 9, 2011, 14 months later, another explosion rocked Sylmar, resulting in traumatic injuries to the owner’s second son, an off-duty Los Angeles firefighter, who lost a leg and part of an arm. A second employee was also severely injured in this blast. In a report issued by Strategic Sciences, Inc., in conjunction with the Environmental Protection Agency (EPA), there have been at least four explosions related to the Symlar process. Two unreported explosions occurred in 2008, followed by the 2010 fatal explosion and the 2011 detonation at Sylmar where two employees were critically injured.

Symlar was making “Brown Gas,” also dubbed “Boom Gas,” by the German inventor who developed the initial process of electrolysis. Brown Gas is essentially a two/one hydrogen/oxygen mixture. This gas is also referred to as “Knallgas”; Sylmar called its gas “Tylar.” This gas was produced through Sylmar’s own patented process and then compressed into high-pressure cylinders for storage and use. This mixture of hydrogen and oxygen is extremely sensitive. Just the friction from opening a valve could be enough to ignite the mixture. Because oxygen is a component inside the cylinder, the flame could also backfire into the cylinder and cause a detonation.

After the 2011 incident, the EPA stepped in to oversee operations to make safe the other compressed cylinders still in existence in the Sylmar plant. A joint “render safe” operation was done in cooperation with the FBI, Los Angeles (CA) Police Department, Anaheim (CA) Police Department, San Bernardino County (CA) Sheriff’s Department, Department of Transportation, California Occupational Safety and Health Administration, California Highway Patrol, Los Angeles County (CA) Fire Department, and Los Angeles Fire Department. Several unaffected cylinders were transported on September 15, 2011, under special U.S. EPA permit, to a safe location and were remotely shot with a 0.308 rifle using steel tip rounds. One of the cylinders detonated after being breached. The others were believed to be empty. Another four cylinders were transported to the China Lake Naval Weapons Station test area, where a bunker was destroyed when one of the cylinders detonated during the render safe operation.

As the cost of fossil fuels rise, there are many who will search for easier and less expensive ways to produce fuel gas. You would not have to look very far to find the home hobbyist who has built some kind of system to make his car run more efficiently. Many inventions, processes, and instructions on how to make fuel at home are available and can be accessed through the Internet, YouTube, and other media by individuals who want to save money and resources. Some of these processes are relatively harmless; others can endanger human life and property.

In September 2013, the Orlando Fire Department responded to one of those processes where an inventor who wanted to make an alternative fuel experienced an incident that could have caused the loss of several lives. Home inventors and start-up companies will continue to experiment in your communities, sometimes with tragic results. All public safety agencies need to be aware of the dangers as they respond to fires and explosions of unknown origins and take special precautions, especially if you are aware that someone is experimenting with fuels in your response community.

Bibliography

1. “1 Dead, 1 Hurt In Menlo Park Explosion and Fire”; http://sanfrancisco.cbslocal.com/2011/09/02/1-dead-2-hurt-in-menlo-park-explosion-fire/; September 2, 2011.

2. “Authorities Identify Man Killed in SIMI Valley Explosion; Death Ruled Accidental”; http://www.vcstar.com/news/2010/jun/18/authorities-identify-man-killed-in-semi-valley/; Foxman, Adam; June 18, 2010.

3. “Los Angeles Gas Explosion Injures Two”; http://www.californiapersonalinjurylawersblog.com/2011/01/los-angeles-gas-explosion-inju.html; Walch, Robert; January 12, 2011.

4. “Orlando Explosion Caused by Experimental Fuel in Vacant Warehouse; 2 Amtrak Trains Delayed for Hours in Aftermath.” http://articles.orlandosentinel.com/2013-09-26/news/os-possible-explosion-orlando-20130926_1_green-fuel-warehouse-tim-roth; Hernandez, Arelis R.; September 26, 2013.

5. “U.S. Department of Transportation Issues First Ever Order to Stop Companies from Transporting Cylinders Filled with Experimental Gas”; U.S. Department of Transportation; November 18, 2011.

6. Avoidance of Failure of Carbon Monoxide and of Carbon Monoxide/Carbon Dioxide Mixtures Cylinders; Second Edition; 2013; Compressed Gas Association.

7. Technical Reference on Hydrogen Compatibility of Materials; Plain Carbon Ferric Steels: C-Mn Alloys (code 1100); Editors: C. San Marchi, B.P. Somerday, Sandia National Laboratories, Livermore, CA.

8. “Hydrogen Compatibility of Materials”; Chris San Marchi, Sandia National Laboratories; DOE EERE Fuel Cell Technologies Office Webinar; August 13, 2013.

9. “Explosion Characteristics of Hydrogen-Air and Hydrogen-Oxygen Mixtures at Elevated Pressures”; Schroeder, V., Holtappels, K. Bundesanstalt fur materialforschung und – pruefung (BAM), Unter den Eichen 87, 12205 Berlin, Germany.

10. “Blast at Plant Breaks Windows in Largo Homes.” www.sptimes.com/News/052301/news_pf/TampaBay/Blast_at_plant_breaks.shtml ; Brassfield, Mike, St. Petersburg Times, published May 23, 2001.

11. “Alternate Fuel Ponzi Scheme Cylinder Render Safe Removal Action”; Strategic Sciences, Inc. http://www.calcupa.org/presentations/CUPA-2013/295/CUPA-2013-Strategic-Sciences,-Inc-THJ1-Wise.pdf;

12. “CO Stress Corrosion Cracking of Carbon Steel Cylinders”; Chemically Speaking LLC; Ngai, Eugene; December 4, 2013.

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