Patent US0008833
We've noted a couple of times, over the long course of our reportage, that some seemingly-conventional petroleum refining techniques appear actually to have been founded on processes developed originally and long ago to facilitate the conversion of Coal into gaseous and liquid hydrocarbon fuels.
In fact, although due to technical difficulties on our end we can't at the moment track the links down for you, we long ago reported on the development of some pretty sophisticated Coal gasification processes in the late 1800's, one even calling for the use of solar energy to help effect the heating of the Coal.
And, the techniques arising from that early, and even later, work on such Coal processing found their way into employment with that late bloomer, the petroleum production and refining industry; a fact confirmed by the National Academy of Engineering, in their tabulation of the petroleum industry's "Greatest Engineering Achievements of the Twentieth Century", as accessible via:
Petroleum Technologies Timeline - Greatest Engineering Achievements of the Twentieth Century.
They introduce the topic by first noting that:
"When retired railroad conductor Edwin Drake struck oil in 1859 in Titusville, Pennsylvania, he touched off the modern oil industry. For the next 40 years the primary interest in oil was as a source of kerosene, used for lighting lamps. Then came the automobile and the realization that the internal combustion engine ran best on gasoline, a byproduct of the process of extracting kerosene from crude oil. As the demand grew for gasoline to power not only cars but also internal combustion engines of all kinds, chemical engineers honing their refining techniques discovered a host of useful byproducts of crude - and the petrochemical industry was born. Oil had truly become black gold."
Then, in:
"1901 - North America’s first oil gusher blows at the Spindletop field near Beaumont in southeastern Texas, spraying more than 800,000 barrels of crude into the air before it can be brought under control. The strike boosts the yearly oil output in the US from 2,000 barrels in 1859 to more than 65 million barrels by 1901."
And, the very next milestone is:
"1913 - High-pressure hydrogenation process developed: German organic chemist Friedrich Bergius develops a high-pressure hydrogenation process that transforms heavy oil and oil residues into lighter oils, boosting gasoline production. In 1926 IG Farben Industries, where Carl Bosch had been developing similar high-pressure processes, acquires the patent rights to the Bergius process. Bergius and Bosch share a Nobel Prize in 1931."
What they don't tell you, almost of course, is that Bergius, as we documented, for only two examples, in:
West Virginia Coal Association | Bergius 1928 Coal Liquefaction | Research & Development; concerning: "United States Patent 1,669,439 - Process for Distilling and Liquefying Coal; 1928; Inventor: Friedrich Bergius, of Heidelberg, Germany"; and:
West Virginia Coal Association | CoalTL Wins Nobel Prize - in 1931 | Research & Development;
had developed his "high-pressure hydrogenation process" originally, as the Nobel Committee's presentation speech has it, for the "manufacture of oils and liquid fuels from solid coal".
Following that, the Academy of Engineering makes note of:
"1920's - Fischer-Tropsch method: By using fractional distillation, two German coal researchers create synthetic gasoline. Known as the Fischer-Tropsch method, the gasoline is produced by combining either coke and steam or crushed coal and heavy oil, then exposing the mixture to a catalyst to form synthetic gasoline. The process plays a critical role in helping to meet the increasing demand for gasoline as automobiles come into widespread use and later for easing gasoline shortages during World War II".
We've made many reports concerning "the Fischer-Tropsch method"; but, for a general narrative, see:
Fischer–Tropsch process - Wikipedia, the free encyclopedia; "The Fischer–Tropsch process ... converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. The process, a key component of gas to liquids technology, produces a synthetic lubrication oil and synthetic fuel, typically from coal".
And, the upshot is that those early technologies, developed originally for the conversion of Coal into useful hydrocarbon liquids and gases, were refined and integrated into the modern petroleum refining industry.
That fact is further confirmed, with the inclusion of perhaps more surprising information, in an article from the American Chemical Society's April, 2001, edition of their official publication, Chemical Innovation:
An environmentally friendly oil industry;
The piece, "An Environmentally Friendly Oil Industry", almost irresistibly snide comments about the title aside, as authored by one "Nai Y. Chen", who spent "34 years as a scientist with Mobil Research & Development Corporation and "holds more than 126 U.S. patents", notes, among other things, that:
"The oil industry ... provided the fuels that powered the engine of industrialization more than 100 years ago, (and, the) first oil refining process was invented to upgrade “coal oil” more than 150 years ago, before Edwin L. Drake touched off a boom with his discovery of oil in Pennsylvania."
And, given that, we thought it might be entertaining to have a look at the Coal liquefaction and Coal liquid refining process that, in point of fact, along with the Bergius and Fischer-Tropsch processes, helped to empower, and to enable the rise of, Big Oil.
Comment follows excerpts from the initial link in this dispatch, concerning the technology, as identified by footnotes included by former Mobil Research & Development Corporation scientist Nai Chen, and specified by him as being the key early innovation in the evolution of the modern petroleum refining industry, to:
"United States Patent 8,833 - Improvement In Making Paraffine-Oil
Patent US8833 - JAMES YOUXG- - Google Patents
March 23, 1852
James Young, Manchester, England
Be it known that I, James Young, of Manchester, England, have invented improvements in the treatment of certain bituminous mineral substances and in obtaining products therefrom; and I do hereby declare the following to be a full, clear, and exact description of the same.
My said invention consists in treating bituminous coals in such manner as to obtain therefrom an oil containing paraffine, (which I call "paraffine-oil,") and from which oil I obtain paraffine. The coals which I deem to be best fitted for this purpose are such as are usually called "parrot-coal", "cannel-coal," and "gas coal," and which are much used in the manufacture of gas for the purpose of illumination, because they yield upon distillation at a high temperature olefiant and other highly illuminating gases in considerable quantity, and although some coals last described contain a large amount of earthy matters, those matters do not interfere materially with the performance of my process.
(In the above, Young is referring to the early, and widespread, "manufactured gas" industry, about which we've reported a few times, as for one example in:
West Virginia Coal Association | Manufactured Gas | Research & Development; "A manufactured gas plant was an industrial facility at which gas was produced from coal, oil and other feedstocks. The gas was stored, and then piped to the surrounding area, where it was used for lighting, cooking, and heating homes and businesses. The first MGPs in New York were constructed in the early 1800s, prior to the Civil War. Most were closed during the early-to-middle 1900s, and the last one ceased operations in 1972. Gas from MGPs was used for all the same purposes that natural gas is used for today. In addition, in the late 1800s, gas was used for lighting prior to the introduction of electricity. For a period of over 100 years, manufactured gas plants (MGPs) were an important part of life in cities and towns throughout New York State and the United States as a whole. They had their beginnings in the early 1800s, providing small amounts of gas for street lighting systems. By 1900, production had greatly increased, and gas was being widely used for heating and cooking. Two main processes were used to produce the gas. The older and simpler process was coal carbonization. In this process, coal was heated in closed retorts or beehive ovens. Inside these ovens, the coal was kept from burning by limiting its contact with outside air. Volatile constituents of the coal would be driven off as a gas, which was collected, cooled, and purified prior to being piped into the surrounding areas for use. The solid portion of the coal would become a black, granular material called coke. Coke was a valuable fuel for many industrial uses and for home heating, because it burned hotter and more cleanly than ordinary coal. Sometimes, the coke was the primary product, and the gas was a by-product, and the facility was called a coke plant".
For more information on what was, at one time, a major Coal-use industry, see
History of manufactured gas - Wikipedia, the free encyclopedia; "The history of manufactured gas, important for lighting, heating, and cooking purposes throughout most of the nineteenth century and the first half of the 20th century, began with the development of analytical and pneumatic chemistry in the eighteenth century. The manufacturing process typically consisted of the gasification of combustible materials, almost always coal ... . The coal was gasified by heating the coal in enclosed ovens with an oxygen-poor atmosphere. Gases, including hydrogen, methane, carbon monoxide and ethylene, were generated, all of which can be burnt for heating and lighting purposes"; and, perhaps more pertinent to our subject:
Gas Light and Coke Company - Wikipedia, the free encyclopedia; "The Gas Light and Coke Company (also known as the Westminster Gas Light and Coke Company), was a company that made and supplied coal gas and coke. It was located on Horseferry Road in Westminster, London. It is identified as the original company from which British Gas plc is descended. The company was ... incorporated by Royal Charter on 30 April 1812 (and) was the first company set up to supply London with coal gas, and operated the first gas works in the United Kingdom which was also the world's first public gas works".
And, one point that shouldn't be missed is, that, fully two hundred years ago, it was known how to, on a large scale industrial and commercial basis, gasify Coal and, through such gasification, produce both simple hydrocarbon gases, "methane" and "ethylene"; and, a blend of "hydrogen" and "carbon monoxide", which would qualify as hydrocarbon synthesis gas.)
To obtain paraffine-oil from coals I proceed as follows: The coals are to be broken into small pieces of about the size of a hen's egg or less for the purpose of facilitating the operation.
(This was, obviously, in the days before the advent of the Metric system in Europe.)
The coal is then to be put into a common gas retort, to which is a attached a wormpipe passing through a refrigerator, and kept at a temperature of about 55 (degrees) Fahrenheit's thermometer by a stream of cold water.
(First, note that, by 1852, a "gas retort", with an "attached ... wormpipe", in which Coal could be gasified or distilled, was already "common". As far as that description of the equipment goes, any old hill country boy who ever grew a whole field of sweet corn without really having a big family or a stable full of critters to feed will know precisely what it is that's being described.)
The retort, being closed in the usual manner, is then to be gradually heated up to a low red heat, at which it is to be kept until volatile products cease to come off. Care must be taken to keep the temperature of the retort from rising above that of a low red heat, so as to prevent as much as possible the desired products of the process being converted into permanent gas.
(The "permanent gas" would be the "hydrogen, methane", etc., which wouldn't condense into a liquid when cooled down in the "wormpipe".)
The crude paraffine-oil distilled or driven off from the coals as a vapor will be condensed into a liquid in passing through the cold worm-pipe, from which it will fall into a vessel, which must be provided to receive it.
The production of the desired products from a charge of coals in a retort will be known to be finished by the liquid ceasing to run from the worm. The crude product of this process is an oil containing paraffine, which, as I have already stated, I call "paraffine-oil".
This oil will sometimes, upon cooling at a temperature of about 40 degree Fahrenheit, deposit paraffine.
(High-quality wax can be a removed from some Coal liquefaction processes as a valuable by-product, as seen in:
sasolwax - Production Process FT - Waxes and sasolwax - Synthetic Wax; "Sasol Wax produces a wide range of synthetic hard, high melting waxes by means of the Fischer Tropsch process. These synthetic hydrocarbon waxes are sold under the "Sasolwax(R) trade name. The Sasol Wax production process in Sasolburg, South Africa, has been continuously modified and improved over the last 50 years to meet your demands for high quality synthetic waxes and wax related products. The in-house raw materials (coal, air, and steam) are transformed into synthesis gases of constant quality year after year. Using own catalysts and state-of-the-art synthesis technology Sasol Wax produces high purity base components free of sulphur and other impurities. These components are distilled and hydrotreated to produce N-paraffins, waxy oils, paraffin waxes and hard waxes which meet the strictest environmental regulations and are tailored for use in a variety of applications. The products are hydrotreated to meet the strictest standards of International Regulatory bodies. Their properties are modified either chemically or physically to meet the requirements in a wide variety of applications."
Or, if preferred, as seen, for one example, in:
Catalysis Letters, Volume 129, Numbers 1-2 - SpringerLink; "Production of Middle Distillate Through Hydrocracking of Paraffin Wax; 2008; Hydrocracking is a key process in petroleum refining for the conversion of heavy hydrocarbons into a variety of high value fuels such as gasoline ... . Although crude oil has been traditionally used as a heavy hydrocarbon source for the production of middle distillate, Fischer–Tropsch wax has also attracted much attention as an alternate feed for the production of middle distillate. F–T wax is typically composed of n-paraffins (90%) ... (and) production of middle distillate through hydrocracking
of F–T wax has been recognized as an economical and environmentally benign process";
such paraffins, or waxes, derived one way or another from Coal, can be economically "hydrocracked", an established process in petroleum refining art, and made to yield "middle distillate"s, which, as the above article in it's entirety explains, can serve as high-quality Diesel fuel.)
I purify the oil obtained ... in the following manner: I put the oil into a cistern and heat it (by a steam pipe or other means) to a temperature of about 150 Fahrenheit. When thus heated water and other undissolved impurities contained in the oil will separate more readily from it than when cold, and the oil being left in a state of rest and kept warm for about a day, many of those impurities will fall to the bottom of the cistern, and the oil may then be run off into another vessel, leaving the residuum behind. I then proceed to distill the oil, for which operation I prefer to use an iron still with a worm-pipe connected to it passing through a refrigeratory apparatus, as before mentioned, the refrigeratory apparatus being kept at or about 55 F ... .
I heat the still by a fire beneath it, which I keep up until the whole of the oil has been distilled over, and it will be found that the still contains some dry carbonaceous residuum, which should be taken out before the still is again used.
(What Young is describing is a very crude form of what later became known as "fractional distillation", and, he is describing basic processes no doubt immediately familiar in their substance and essentials to modern petroleum refinery engineers and chemists. We won't reproduce the details in our excerpts, but he goes on then at some length concerning the further treatment of the now doubly-distilled Coal liquids with "oil of vitriol", i.e., Sulfuric acid - Wikipedia, the free encyclopedia, "The historical name of this acid is oil of vitriol"; and, then, the neutralization of the acidified Coal liquids with "caustic soda", or lye, all of which serves to react and settle out contaminants; a series of steps which again, as can be learned via: Alkylation in petroleum refining; "Sulfuric Acid Alkylation"; presages some modern petroleum refinery techniques. After the acid treatment and caustic soda neutralization, Young directs that an amount of ground "chalk" be added to the liquid, which would further neutralize, or buffer, the fluid, and the resulting solid, coagulated particles be allowed to settle, before the thus-clarified Coal-derived liquids are drawn off.)
(The resulting oil) is then fit to be used for lubricating purposes ..., or it may be burned ... for the purpose of illumination; and this oil may be further purified, if required, by distilling it over again.
To extract paraffine from the purified paraffine-oil ... the oil is to be cooled to a low temperature - say 30 or 40 degree Fahrenheit - and the lower the temperature the larger will be the quantity of paraffine separated from the oil. In this way paraffine is made to crystallize, and in this state it may be separated from the oil by filtration ... .
Paraffine-oil from which paraffine has been separated, above described, still contains paraffine in solution and is suitable for lubricating or lighting purposes, as already mentioned.
(Or, we submit, for "hydrotreating", a more modern, but now well-established, petroleum refining technique, and further conversion into even more refined, more volatile, and more familiar, hydrocarbon fuels.)
What I claim as my invention (is the) obtaining of paraffine oil, or an oil containing paraffine, and paraffine from bituminous coals."
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And, there you have it:
A basic process and technology, similar in some respects to coking, but without the limited oxidation, established one and one-half centuries ago; a process and technology specifically identified, by an educated and highly-accomplished Mobil Oil Corporation scientist, as being the progenitor of modern petroleum refining technology; a process directed toward:
"obtaining ... an oil containing paraffine ... from bituminous coals".
It's time, ain't it - - far, far past time - - we returned to our roots?
