I was too late to join in the fun, so I decided to start a new post.
I had been putting together a presentation for my son's 6th grade science class on the history of gasoline, and thought I'd throw some more fuel on the fire
In 1856, the worlds first oil refinery opened in Ploeisti, Romania with kerosene the main commercial product, and gasoline a dangerous and almost useless byproduct of the distillation process. In 1876, Nicolaus Otto invented the 4 stroke internal combustion engine, the foundation of all commercially viable gasoline powered automobiles from then on. In the late 1880s when oil was discovered in Pennsylvania, kerosene replaced "camphene" or "burning oil" for use in indoor lighting in the U.S. Gasoline had almost no market and was usually burned off or dumped in the nearest river!
Now the chemical makeup of gasoline is a blend of lengths of hydrocarbon chains that range from 5 to 10 carbon atoms. What distills naturally are mostly straight chains and a fairly even mix of the lighter end of the scale. The short straight chains have a very low flash point, making the raw unprocessed gas extremely volatile (very low octane rating).
In what has to be the most serendipitous event in history, in 1885 Karl Benz patented his invention of the carburetor, the "accelerator", the spark plug, a battery powered ignition system, the clutch and the water cooled radiator. He combined all these inventions to produce the first working gasoline powered vehicle (a 3 wheeler). Goltieb Daimler's carburetor was patented in 1887. Daimler (who worked for Otto) also built a 2 wheeled gasoline powered motorcycle in 1885 (although his boss claims to have built one back in 1876), and the 1st 4 wheeled "car" in 1886. Auto manufacturers started springing up everywhere, and it wasn't long before gasoline beat out kerosene as the primary product of the oil refineries, but it didn't come easy.
On January 10, 1901, Anthony Lucas has his crew install a new drill bit and lowers the drill about 700 feet when they hit a gusher outside Beaumont Texas at what would become known as Spindletop (it was originally two words; Spindle Top, and had been used to quarantine Confederate soldiers with yellow fever; a reporter wrote it incorrectly in the 20s and it stuck). Initially it produced 80,000 barrels of oil per day and yet in 1906, representatives from the Detroit board of Commerce told a US Senate hearing they were not so much worried about the cost of gas as the supply (the sky is falling is a recurring theme in American politics
).
Even with the plentiful supply of crude oil, the gasoline that was produced as a natural byproduct wasn't enough to meet the growing demand of cars being built by the 1910s. Gas was bought at the general store back then, and you brought it home in a bucket. It lit off so easy that it was very dangerous to handle or store, and during the 1910s, most states banned it's storage on residential property, This drove the development of the first commercial gas pumps. The gasoline pump had also been invented in 1885 by Sylvanus Bowser of Fort Wayne, Indiana. They were hand operated, and often it was just a pump set up on the side of the street, with a strapping young lad to operate it.
The octane rating was so low that the engines could only be built with a 4 to 1 compression ratio to keep from blowing itself apart. This made the power to weight ratio pretty lousy. Advances came fast though, and mostly from Americans
. In 1913 William Burton invented the process of thermal cracking; using heat and high pressure to break up longer hydro-carbon chains into smaller ones, thereby converting more of the crude into gasoline. Around 1922, Thomas Midgley Jr. was working on the knocking problem in Kerosene engines by systematically trying one compound after another in an attempt to find something to stop the knocking, and discovered that Tetra-Ethyl Lead solved his problem. His GM engineer buddy Thomas Kettering then added it to gasoline and found he could solve the same problem when the compression was raised higher than normal gasoline engines could tolerate in those days. The goal at that time was to improve the efficiency and increase power by raising compression, but the limiting factor was the low octane rating of the available fuel (ahem, there is absolutely no eveidence that any thought was given to lubricating valves). In 1923, the first Ethyl gasoline was sold at the pump. Now don't think this was without controversy even back then! It was hotly debated, as Ethanol was also known to increase the octane rating, and was being sold in Europe in 10 to 20% ratios as an alternative to Ethyl, and TEL was known to be poisonous. Unfortuantely TEL was much cheaper, so despite the known health risks, the American oil industry chose lead. An article in the October, 1924 'New York Journal-American' declared that 17 Bayway, New Jersey oil refinery workers died "violently insane" as a result of TEL poisoning. For what it's worth, H. Ford opposed TEL, and preffered Ethanol instead. This was probably as much because it was a GM product as anything, but Ford was also genuinely concerned about the plight of farmers who were in an economic crisis in 1925, and he saw growing corn for ethanol as killing two birds with one stone. By the mid 30s, Kettering had joined Ford and T. Eddison in a campaign to promote Ethanol as the long term solution.
Back to gasoline production: in 1923 the first commercially successful catalytic cracking process was invented by Almer McDuffie McAfee. The octane rating of the mid 1920s cracked Ethyl gas ranged from 40 to 60, allowing compression ratios in the 6:1 range (perhaps 7:1 at best). In 1937 Eugene Houdry invented the catalytic process of cracking low grade fuel into high grade fuel, allowing an increase in compression to around 8:1 and more power output. Also developed in the 30s was Polymerization, which attacks the production problem from the other end, taking lighter propylene and butylene chains and forming longer ones in the gasoline range. Isomerization converted the naturally occurring straight chains into branched chains, and thereby increasing the octane rating.
During WWII, hi octane aviation fuel was needed in mass quantities, and increasing TEL was the easiest way to get there. In the 50s, more lead was added to automotive gas, and hydrocracking was invented, both of which increased the octane rating and potential power output as Detroit continued to build ever more powerful, higher compression engines. In 1960, the zeolite catalyst was patented by Charles Plank and Ed Rosinski, which broke down long chains into shorter ones, further increasing the amount of crude oil that could be converted into gasoline.
When lead was phased out in the 70s, there was an initial drop of high grade gas, as chemically rearanging the molecules was just about the only way to increase the octane rating. Just as branched chains were superior to straight chains, it was discovered in the early 80s that tying the ends of an 8 carbon atom chain together created what is called an "octet" and produced a very high octane rating without the need for additives. We now have 93 to 94 octane unleaded gas on almost every street corner.
Due to the environmental regulations and requirements, no new oil refineries have been built in the US since 1976. This has lead to increasing the amount of refined gasoline we must now import instead of crude oil to meet demand. This also makes our gasoline supply more unstable, and subject to wild spikes in price.
I realize that the blood fued over TEL and valve lubrication seems to be settled, and this is not intended to be a slam on anyone, but I will add this: I am willing to accept what I've been told by multiple old time machine shops, and that is on normal daily driver engines, with the loss of leaded fuels, there was a noticeable increase in exhaust valves being sunken into the head on pre unleaded design engines, regardless of the original design intent of Ethyl gasoline. It could be coincidence, and yes earlier cars didn't drive 100K miles before being retired, but you would have to find an unmolested, well documented, pre '23 engine to disect to look for evidence of valves sinking into heads before the introduction of TEL. If I took the approach that everything must be proven to me in a controlled experiment before I will accept it, I would be paralyzed into inaction. I rely on the expertise and experience of others to make judgements that allow me to increase the probability of success.
There were too many sources to reference, but Wickepedia and About were the two primary sources. Some references were contradictory in the fine details so I picked what I thought was the best fit, but everything I have stated can be verified by simply googling.
I'm also not a tree hugger, but I'm glad we finally got the lead out. I am an engineer, physicist, carpenter, gearhead and history buff... and the big oil companies ARE evil
I had been putting together a presentation for my son's 6th grade science class on the history of gasoline, and thought I'd throw some more fuel on the fire
In 1856, the worlds first oil refinery opened in Ploeisti, Romania with kerosene the main commercial product, and gasoline a dangerous and almost useless byproduct of the distillation process. In 1876, Nicolaus Otto invented the 4 stroke internal combustion engine, the foundation of all commercially viable gasoline powered automobiles from then on. In the late 1880s when oil was discovered in Pennsylvania, kerosene replaced "camphene" or "burning oil" for use in indoor lighting in the U.S. Gasoline had almost no market and was usually burned off or dumped in the nearest river!
Now the chemical makeup of gasoline is a blend of lengths of hydrocarbon chains that range from 5 to 10 carbon atoms. What distills naturally are mostly straight chains and a fairly even mix of the lighter end of the scale. The short straight chains have a very low flash point, making the raw unprocessed gas extremely volatile (very low octane rating).
In what has to be the most serendipitous event in history, in 1885 Karl Benz patented his invention of the carburetor, the "accelerator", the spark plug, a battery powered ignition system, the clutch and the water cooled radiator. He combined all these inventions to produce the first working gasoline powered vehicle (a 3 wheeler). Goltieb Daimler's carburetor was patented in 1887. Daimler (who worked for Otto) also built a 2 wheeled gasoline powered motorcycle in 1885 (although his boss claims to have built one back in 1876), and the 1st 4 wheeled "car" in 1886. Auto manufacturers started springing up everywhere, and it wasn't long before gasoline beat out kerosene as the primary product of the oil refineries, but it didn't come easy.
On January 10, 1901, Anthony Lucas has his crew install a new drill bit and lowers the drill about 700 feet when they hit a gusher outside Beaumont Texas at what would become known as Spindletop (it was originally two words; Spindle Top, and had been used to quarantine Confederate soldiers with yellow fever; a reporter wrote it incorrectly in the 20s and it stuck). Initially it produced 80,000 barrels of oil per day and yet in 1906, representatives from the Detroit board of Commerce told a US Senate hearing they were not so much worried about the cost of gas as the supply (the sky is falling is a recurring theme in American politics
). Even with the plentiful supply of crude oil, the gasoline that was produced as a natural byproduct wasn't enough to meet the growing demand of cars being built by the 1910s. Gas was bought at the general store back then, and you brought it home in a bucket. It lit off so easy that it was very dangerous to handle or store, and during the 1910s, most states banned it's storage on residential property, This drove the development of the first commercial gas pumps. The gasoline pump had also been invented in 1885 by Sylvanus Bowser of Fort Wayne, Indiana. They were hand operated, and often it was just a pump set up on the side of the street, with a strapping young lad to operate it.
The octane rating was so low that the engines could only be built with a 4 to 1 compression ratio to keep from blowing itself apart. This made the power to weight ratio pretty lousy. Advances came fast though, and mostly from Americans
. In 1913 William Burton invented the process of thermal cracking; using heat and high pressure to break up longer hydro-carbon chains into smaller ones, thereby converting more of the crude into gasoline. Around 1922, Thomas Midgley Jr. was working on the knocking problem in Kerosene engines by systematically trying one compound after another in an attempt to find something to stop the knocking, and discovered that Tetra-Ethyl Lead solved his problem. His GM engineer buddy Thomas Kettering then added it to gasoline and found he could solve the same problem when the compression was raised higher than normal gasoline engines could tolerate in those days. The goal at that time was to improve the efficiency and increase power by raising compression, but the limiting factor was the low octane rating of the available fuel (ahem, there is absolutely no eveidence that any thought was given to lubricating valves). In 1923, the first Ethyl gasoline was sold at the pump. Now don't think this was without controversy even back then! It was hotly debated, as Ethanol was also known to increase the octane rating, and was being sold in Europe in 10 to 20% ratios as an alternative to Ethyl, and TEL was known to be poisonous. Unfortuantely TEL was much cheaper, so despite the known health risks, the American oil industry chose lead. An article in the October, 1924 'New York Journal-American' declared that 17 Bayway, New Jersey oil refinery workers died "violently insane" as a result of TEL poisoning. For what it's worth, H. Ford opposed TEL, and preffered Ethanol instead. This was probably as much because it was a GM product as anything, but Ford was also genuinely concerned about the plight of farmers who were in an economic crisis in 1925, and he saw growing corn for ethanol as killing two birds with one stone. By the mid 30s, Kettering had joined Ford and T. Eddison in a campaign to promote Ethanol as the long term solution. Back to gasoline production: in 1923 the first commercially successful catalytic cracking process was invented by Almer McDuffie McAfee. The octane rating of the mid 1920s cracked Ethyl gas ranged from 40 to 60, allowing compression ratios in the 6:1 range (perhaps 7:1 at best). In 1937 Eugene Houdry invented the catalytic process of cracking low grade fuel into high grade fuel, allowing an increase in compression to around 8:1 and more power output. Also developed in the 30s was Polymerization, which attacks the production problem from the other end, taking lighter propylene and butylene chains and forming longer ones in the gasoline range. Isomerization converted the naturally occurring straight chains into branched chains, and thereby increasing the octane rating.
During WWII, hi octane aviation fuel was needed in mass quantities, and increasing TEL was the easiest way to get there. In the 50s, more lead was added to automotive gas, and hydrocracking was invented, both of which increased the octane rating and potential power output as Detroit continued to build ever more powerful, higher compression engines. In 1960, the zeolite catalyst was patented by Charles Plank and Ed Rosinski, which broke down long chains into shorter ones, further increasing the amount of crude oil that could be converted into gasoline.
When lead was phased out in the 70s, there was an initial drop of high grade gas, as chemically rearanging the molecules was just about the only way to increase the octane rating. Just as branched chains were superior to straight chains, it was discovered in the early 80s that tying the ends of an 8 carbon atom chain together created what is called an "octet" and produced a very high octane rating without the need for additives. We now have 93 to 94 octane unleaded gas on almost every street corner.
Due to the environmental regulations and requirements, no new oil refineries have been built in the US since 1976. This has lead to increasing the amount of refined gasoline we must now import instead of crude oil to meet demand. This also makes our gasoline supply more unstable, and subject to wild spikes in price.
I realize that the blood fued over TEL and valve lubrication seems to be settled, and this is not intended to be a slam on anyone, but I will add this: I am willing to accept what I've been told by multiple old time machine shops, and that is on normal daily driver engines, with the loss of leaded fuels, there was a noticeable increase in exhaust valves being sunken into the head on pre unleaded design engines, regardless of the original design intent of Ethyl gasoline. It could be coincidence, and yes earlier cars didn't drive 100K miles before being retired, but you would have to find an unmolested, well documented, pre '23 engine to disect to look for evidence of valves sinking into heads before the introduction of TEL. If I took the approach that everything must be proven to me in a controlled experiment before I will accept it, I would be paralyzed into inaction. I rely on the expertise and experience of others to make judgements that allow me to increase the probability of success.
There were too many sources to reference, but Wickepedia and About were the two primary sources. Some references were contradictory in the fine details so I picked what I thought was the best fit, but everything I have stated can be verified by simply googling.
I'm also not a tree hugger, but I'm glad we finally got the lead out. I am an engineer, physicist, carpenter, gearhead and history buff... and the big oil companies ARE evil
Just kidding. 
