Thermal cracking process

The invention: 



Process that increased the yield of refined gasoline

extracted from raw petroleum by using heat to convert complex

hydrocarbons into simpler gasoline hydrocarbons, thereby making

possible the development of the modern petroleum industry.



The people behind the invention:



William M. Burton (1865-1954), an American chemist

Robert E. Humphreys (1942- ), an American chemist










Gasoline, Motor Vehicles, and Thermal Cracking



Gasoline is a liquid mixture of hydrocarbons (chemicals made up

of only hydrogen and carbon) that is used primarily as a fuel for internal

combustion engines. It is produced by petroleum refineries

that obtain it by processing petroleum (crude oil), a naturally occurring

mixture of thousands of hydrocarbons, the molecules of which

can contain from one to sixty carbon atoms.

Gasoline production begins with the “fractional distillation” of

crude oil in a fractionation tower, where it is heated to about 400 degrees

Celsius at the tower’s base. This heating vaporizes most of the

hydrocarbons that are present, and the vapor rises in the tower,

cooling as it does so. At various levels of the tower, various portions

(fractions) of the vapor containing simple hydrocarbon mixtures become

liquid again, are collected, and are piped out as “petroleum

fractions.” Gasoline, the petroleum fraction that boils between 30

and 190 degrees Celsius, is mostly a mixture of hydrocarbons that

contain five to twelve carbon atoms.

Only about 25 percent of petroleum will become gasoline via

fractional distillation. This amount of “straight run” gasoline is not

sufficient to meet the world’s needs. Therefore, numerous methods

have been developed to produce the needed amounts of gasoline.

The first such method, “thermal cracking,” was developed in 1913

by William M. Burton of Standard Oil of Indiana. Burton’s cracking

process used heat to convert complex hydrocarbons (whose molecules

contain many carbon atoms) into simpler gasoline hydrocarbons

(whose molecules contain fewer carbon atoms), thereby increasing

the yield of gasoline from petroleum. Later advances in

petroleum technology, including both an improved Burton method

and other methods, increased the gasoline yield still further.





More Gasoline!



Starting in about 1900, gasoline became important as a fuel for

the internal combustion engines of the new vehicles called automobiles.

By 1910, half a million automobiles traveled American roads.

Soon, the great demand for gasoline—which was destined to grow

and grow—required both the discovery of new crude oil fields

around the world and improved methods for refining the petroleum

mined from these new sources. Efforts were made to increase

the yield of gasoline—at that time, about 15 percent—from petroleum.

The Burton method was the first such method.

At the time that the cracking process was developed, Burton was

the general superintendent of the Whiting refinery, owned by Standard

Oil of Indiana. The Burton process was developed in collaboration

with Robert E. Humphreys and F. M. Rogers. This three-person

research group began work knowing that heating petroleum

fractions that contained hydrocarbons more complex than those

present in gasoline—a process called “coking”—produced kerosene,

coke (a form of carbon), and a small amount of gasoline. The

process needed to be improved substantially, however, before it

could be used commercially.

Initially, Burton and his coworkers used the “heavy fuel” fraction

of petroleum (the 66 percent of petroleum that boils at a temperature

higher than the boiling temperature of kerosene). Soon, they

found that it was better to use only the part of the material that contained

its smaller hydrocarbons (those containing fewer carbon atoms),

all of which were still much larger than those present in gasoline.

The cracking procedure attempted first involved passing the

starting material through a hot tube. This hot-tube treatment vaporized

the material and broke down 20 to 30 percent of the larger hydrocarbons

into the hydrocarbons found in gasoline. Various tarry

products were also produced, however, that reduced the quality of

the gasoline that was obtained in this way.



Next, the investigators attempted to work at a higher temperature

by bubbling the starting material through molten lead. More

gasoline was made in this way, but it was so contaminated with

gummy material that it could not be used. Continued investigation

showed, however, that moderate temperatures (between those used

in the hot-tube experiments and that of molten lead) produced the

best yield of useful gasoline.

The Burton group then had the idea of using high pressure to

“keep starting materials still.” Although the theoretical basis for the

use of high pressure was later shown to be incorrect, the new

method worked quite well. In 1913, the Burton method was patented

and put into use. The first cracked gasoline, called Motor

Spirit, was not very popular, because it was yellowish and had a

somewhat unpleasant odor. The addition of some minor refining

procedures, however, soon made cracked gasoline indistinguishable

from straight run gasoline. Standard Oil of Indiana made huge

profits from cracked gasoline over the next ten years. Ultimately,

thermal cracking subjected the petroleum fractions that were

utilized to temperatures between 550 and 750 degrees Celsius, under

pressures between 250 and 750 pounds per square inch.



Impact



In addition to using thermal cracking to make gasoline for sale,

Standard Oil of Indiana also profited by licensing the process for use

by other gasoline producers. Soon, the method was used throughout

the oil industry. By 1920, it had been perfected as much as it

could be, and the gasoline yield from petroleum had been significantly

increased. The disadvantages of thermal cracking include a

relatively low yield of gasoline (compared to those of other methods),

the waste of hydrocarbons in fractions converted to tar and

coke, and the relatively high cost of the process.

A partial solution to these problems was found in “catalytic

cracking”—the next logical step from the Burton method—in which

petroleum fractions to be cracked are mixed with a catalyst (a substance

that causes a chemical reaction to proceed more quickly,

without reacting itself). The most common catalysts used in such

cracking were minerals called “zeolites.” The wide use of catalytic

cracking soon enabled gasoline producers to work at lower temperatures

(450 to 550 degrees Celsius) and pressures (10 to 50 pounds

per square inch). This use decreased manufacturing costs because

catalytic cracking required relatively little energy, produced only

small quantities of undesirable side products, and produced high quality

gasoline.

Various other methods of producing gasoline have been developed—

among them catalytic reforming, hydrocracking, alkylation,

and catalytic isomerization—and now about 60 percent of the petroleum

starting material can be turned into gasoline. These methods,

and others still to come, are expected to ensure that the world’s

needs for gasoline will continue to be satisfied—as long as petroleum

remains available.



See also: Fuel cell; Gas-electric car; Geothermal power; Internal

combustion engine; Oil-well drill bit; Solar thermal engine.

Teflon

The invention: 



Afluorocarbon polymer whose chemical inertness
and physical properties have made it useful for many applications,
from nonstick cookware coatings to suits for astronauts.


The person behind the invention:


Roy J. Plunkett (1910-1994), an American chemist










Nontoxic Refrigerant Sought


As the use of mechanical refrigeration increased in the late 1930’s,
manufacturers recognized the need for a material to replace sulfur
dioxide and ammonia, which, although they were the commonly
used refrigerants of the time, were less than ideal for the purpose.
The material sought had to be nontoxic, odorless, colorless, and not
flammable. Thomas Midgley, Jr., and Albert Henne of General Motors
Corporation’s Frigidaire Division concluded, from studying
published reports listing properties of a wide variety of chemicals,
that hydrocarbon-like materials with hydrogen atoms replaced by
chlorine and fluorine atoms would be appropriate.
Their conclusion led to the formation of a joint effort between the
General Motors Corporation’s Frigidaire Division and E. I. Du Pont
de Nemours to research and develop the chemistry of fluorocarbons.
In this research effort, a number of scientists began making
and studying the large number of individual chemicals in the general
class of compounds being investigated. It fell to Roy J. Plunkett
to do a detailed study of tetrafluoroethylene, a compound consisting
of two carbon atoms, each of which is attached to the other as
well as to two fluorine atoms.



The “Empty” Tank


Tetrafluoroethylene, at normal room temperature and pressure,
is a gas that is supplied to users in small pressurized cylinders. On
the morning of the day of the discovery, Plunkett attached such a
tank to his experimental apparatus and opened the tank’s valve. To

his great surprise, no gas flowed from the tank. Plunkett’s subsequent
actions transformed this event from an experiment gone
wrong into a historically significant discovery. Rather than replacing
the tank with another and going on with the work planned for
the day, Plunkett, who wanted to know what had happened, examined
the “empty” tank. When he weighed the tank, he discovered
that it was not empty; it did contain the chemical that was listed on
the label. Opening the valve and running a wire through the opening
proved that what had happened had not been caused by a malfunctioning
valve. Finally, Plunkett sawed the cylinder in half and
discovered what had happened. The chemical in the tank was no
longer a gas; instead, it was a waxy white powder.
Plunkett immediately recognized the meaning of the presence of
the solid. The six-atom molecules of the tetrafluoroethylene gas had
somehow linked with one another to form much larger molecules.
The gas had polymerized, becoming polytetrafluoroethylene, a solid
with a high molecular weight. Capitalizing on this occurrence,
Plunkett, along with other Du Pont chemists, performed a series of
experiments and soon learned to control the polymerization reaction
so that the product could be produced, its properties could be
studied, and applications for it could be developed.
The properties of the substance were remarkable indeed. It was
unaffected by strong acids and bases, withstood high temperatures
without reacting or melting, and was not dissolved by any solvent
that the scientists tried. In addition to this highly unusual behavior,
the polymer had surface properties that made it very slick. It was so
slippery that other materials placed on its surface slid off in much
the same way that beads of water slide off the surface of a newly
waxed automobile.

Although these properties were remarkable, no applications were
suggested immediately for the new material. The polymer might
have remained a laboratory curiosity if a conversation had not
taken place between Leslie R. Groves, the head of the Manhattan
Project (which engineered the construction of the first atomic bombs),
and a Du Pont chemist who described the polymer to him. The
Manhattan Project research team was hunting for an inert material
to use for gaskets to seal pumps and piping. The gaskets had to be
able to withstand the highly corrosive uranium hexafluoride with

which the team was working. This uranium compound is fundamental
to the process of upgrading uranium for use in explosive devices
and power reactors. Polytetrafluoroethylene proved to be just
the material that they needed, and Du Pont proceeded, throughout
World War II and after, to manufacture gaskets for use in uranium
enrichment plants.
The high level of secrecy of the Manhattan Project in particular
and atomic energy in general delayed the commercial introduction
of the polymer, which was called Teflon, until the late 1950’s. At that
time, the first Teflon-coated cooking utensils were introduced.



Impact


Plunkett’s thoroughness in following up a chance observation
gave the world a material that has found a wide variety of uses, ranging
from home kitchens to outer space. Some applications make use

of Teflon’s slipperiness, othersmake use of its inertness, and others take

advantage of both properties.
The best-known application of Teflon is as a nonstick coating for cookware.
Teflon’s very slippery surface initially was troublesome, when it proved to be
difficult to attach to other materials. Early versions of Teflon-coated cookware

shed their surface coatings easily, even when care was taken to avoid scraping it off.

A suitable bonding process was soon developed, however, and the present coated

surfaces are very rugged and provide a noncontaminating coating that can be cleaned
easily.
Teflon has proved to be a useful material in making devices that
are implanted in the human body. It is easily formed into various
shapes and is one of the few materials that the human body does not
reject. Teflon has been used to make heart valves, pacemakers, bone
and tendon substitutes, artificial corneas, and dentures.
Teflon’s space applications have included its use as the outer skin
of the suits worn by astronauts, as insulating coating on wires and
cables in spacecraft that must resist high-energy cosmic radiation,
and as heat-resistant nose cones and heat shields on spacecraft.

Roy J. Plunkett






Roy J. Plunkett was born in 1910 in New Carlisle, Ohio. In
1932 he received a bachelor’s degree in chemistry from Manchester
College and transferred to Ohio State University for
graduate school, earning a master’s degree in 1933 and a doctorate
in 1936. The same year he went to work for E. I. Du Pont
de Nemours and Company as a research chemist at the Jackson
Laboratory in Deepwater, New Jersey. Less then two years later,
when he was only twenty-seven years old, he found the strange
polymer tetrafluoroethylene, whose trade name became Teflon.
It would turn out to be among Du Pont’s most famous products.
In 1938 Du Pont appointed Plunkett the chemical supervisor
at its largest plant, the Chamber Works in Deepwater, which
produced tetraethyl lead. He held the position until 1952 and
afterward directed the company’s Freon Products Division. He
retired in 1975. In 1985 he was inducted into the Inventor’s Hall
of Fame, and after his death in 1994, Du Pont created the
Plunkett Award, presented to inventors who find new uses for
Teflon and Tefzel, a related fluoropolymer, in



See also :



Buna rubber; Neoprene; Nylon; Plastic; Polystyrene;