Refining Overview Part 2 Development of the Modern Refinery

Chapter 5 The Age of the Thermal Refinery

CHAPTER 5
THE AGE OF THE THERMAL REFINERY
1910-1940
Chapter 4
Primitive Refinery

Chapter 5
Thermal Refinery

Chapter 6
Catalytic Refinery

1840 1910

1910 1940

1940 1970

Chapter 7
End of the Century
Refinery
1970 2000

The Advent of the Age of the Thermal Refinery

The refineries built to process the new sources of crude oil found in Texas in 1901 responded to the rapidly
changing market demand picture. The advent of the automobile sharply increased the demand for gasoline. In
1896 it is estimated there were four automobiles in the U.S. that could run reliably. In two years the number
increased to 800. In 1905 Olds turned out 6300 of his famous one-cylinder Oldsmobiles. By 1910, reflecting
the addition of Ford's Tin Lizzie, the Model T to the market in 1908, there were almost 500,000 registered
automobiles. Remarkably, the air age was also incubating. Just before Christmas on December 17, 1901, on a
sandy beach at Kitty Hawk, North Carolina, Wilbur and Orville Wright first flew their plane 120 feet.
Refiners recognized that production of kerosene and gasoline in the quantities that would be sold soon could not
be met by running more crude oil. The crude oil was available but there was not nearly near enough disposal
capacity (creeks and burn pits) for the unwanted "byproducts."
It should be noted that there was another revolutionary development at the turn of the century - electricity. The
impact of the electric light on kerosene for illumination was not as dramatic as the impact of the automobile on
the need for gasoline. But even as refiners resorted to cracking to make more kerosene, the demand began to
slip. After Edison patented the electric light bulb in 1879, electricity became more common in metropolitan
areas. The demand for kerosene continued in rural areas, though, because electric power distribution outside the
urban areas was almost non-existent. Nonetheless, kerosene would fade from the scene until the jet engine
revived demand in a later age.
The answer to the demand for the lighter fractions, both gasoline and kerosene, lay in cracking the heavier gas
oil portion of the barrel. The evolution of refining in the first two decades of the 20th century was defined in
terms of various thermal cracking developments although treating processes became more important due to
cracking.
Technology Developments
The Burton Thermal Cracking Batch Process for Gas Oil to Increase Gasoline Yield
The important developments were in the area of thermal cracking. Initially it was thought necessary to vaporize
the oil before cracking but attempts at vapor phase cracking were not successful. It came to be recognized that a
thin film of oil on the tubes coked leading to plugging. It should be noted that so called experimentation and
research was frequently conducted in the refinery, many of which typically still had a capacity of only a few
thousand barrels per day.
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Refining Overview Part 2 Development of the Modern Refinery

Chapter 5 The Age of the Thermal Refinery

Dr. William M.
Burton
1865 1954
Reprinted by permission from
Petroleum Refiner January
1959, Copyright 1959, Gulf
Publishing Co, All Rights
Reserved

But in 1912 William M. Burton announced his new liquid gas oil cracking process. It
was installed first by Standard Oil of Indiana at Whiting. (By this time, the US
Supreme Court had issued a decree in September 1911 to split up Standard Oil of
New Jersey.) The process was a 150 barrel batch operation, charging gas oil at 75
psig pressure and 750F, heating and distilling in a 48-hour cycle until half of the
charge was broken down into lighter components. The vapors rose from the still into
a high-pressure chamber. Liquid condensed on the walls and cracked as it drained
back to the still. The overhead vapor was condensed and the liquid was let down in a
two step process that produced dry gas and then wet gas and cracked liquid. In 1913,
Standard Oil, recognizing that it gave higher performance because of the gasoline's
olefin and aromatic content, and that is could be sold for 3 cents less a gallon than
straight run gasoline, sold a blend containing Burton naphtha as "motor spirit." In the
same year, Standard Oil installed an additional 60 cracking units at the Whiting
refinery.
Pressures were increased to as high as 300 psig with correspondingly higher
temperatures. This increased the gasoline yield from the gas oil charge to 30% from
15%. Dr. Burton was recognized for his basic contribution of liquid cracking to
petroleum technology with awards from American Chemical Society and Society of
the Chemical Industry. But the process needed improvement. That came from
another Standard Oil Company's application of the Burton process.

The Burton-Clark Thermal Batch Cracking Process for Gas Oil

In 1921, E. M. Clark of Standard Oil of New Jersey patented the Burton-Clark circulating heater process.
Burton-Clark Batch Thermal Cracking Furnace
Circa 1923
Bubble Tray Tower
(non refluxed)
Water
Condenser

Hydrogen, methane, ethane

Kettle
Still

Ethane, propane
flue

Feed In
Fire Box

High Pressure
Separator

Gasoline, kerosene

(coal fired)
Tar Out

Tube Cracking Furnace thermosyphon

Low Pressure Separator

Adapted from Oil and Gas Journal. Reprinted by permission,

January 1959, Copyright 1959, PennWell Corp, All Rights
Reserved

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Refining Overview Part 2 Development of the Modern Refinery

Chapter 5 The Age of the Thermal Refinery

This employed tubular heating similar to a steam boiler in that the firebox did not have to transmit heat
exclusively to the bottom of the horizontal drum holding the charge of gas oil to be cracked. Clark provided a
series of tubes in the firebox that circulated hot gas oil back to the drum by thermal convection. The hot gases
from the coal-fired furnace flowed up over the high end of the tubes and down over the low end of the slanted
bundle. Feed was introduced in the low end of the tubes and tar was withdrawn from the bottom set of tubes.
The capacity of a typical Burton installation was more than doubled by Clark's improvement in surface area.
Other Variations
Almost every major refiner had its own variant, covered by a patent claiming some novel feature or virtue.
Universal Oil Products perfected and licensed the Dubbs Process developed by Jesse Dubbs and his son Carbon
Petroleum Dubbs. The Dubbs process involved tubular heating to high temperatures at high pressures followed
by letdown in a series of larger tubes, which were later replaced by a soaker drum. Vapors from the soaker
drum were routed to a dephlegmator where the overhead was condensed and reluxed back to the dephlegmator.
Bottoms from the dephlegmator were mixed with the feed. Condensed distillate was sent to fractionation. The
first unit was licensed and installed by Roxana Oil (Shell) at the Wood River, Illinois in 1921. It operated at
125 psig and had a capacity of 250 barrels/day. The Texas Company (Texaco) installed the Holmes-Manley
process at Port Arthur, Texas in 1917 and added another 24 batteries of 4 stills each in 1920. They operated at
175 psig. Gasoline Products licensed the Cross process,
developed by Walter M. Cross and Roy Cross of Kansas
City. The first was built in 1920. It operated at 600 psig.
There were other processes developed many by oil
companies such as Gulf Refining.

Dubbs Still, Roxana (Shell) Refinery, Wood

River, Illinois, 1921
Holmes-Manley, The Texas Company, Port
Arthur, Texas, circa 1920

Reprinted by permission from Petroleum Refiner, January 1959,

Copyright 1959, Gulf Publishing Co, All Rights Reserved

Reprinted by permission from Petroleum Refiner, January 1959,

Copyright 1959, Gulf Publishing Co, All Rights Reserved

The Patent Wars

Several cracking patent infringement cases arose in the twenties, as companies vied for a privileged position in
thermal cracking, the new process that increased the yield of gasoline. The most famous was Universal Oil
Products' suit against Standard Oil of Indiana for infringement of the Dubbs patent. The Dubbs patent covered
work done by Jesse Dubbs and his son Carbon Petroleum Dubbs. UOP owned the patent and eventually sold it
to Shell. The reasoning for Dubbs' novelty and infringement by Standard were obscure and complex and the
trial, held in St. Louis, was a prolonged one with many experts testifying for each side. The trial pitted two of
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Chapter 5 The Age of the Thermal Refinery

the most renowned experts of the age: Dr. Gustav Egloff

of Universal Oil Products and Carbon Petroleum Dubbs of
Standard Oil.

Dr. Gustav Egloff

1885 1955

Dr. Gustav Egloff, known in the industry as Gasoline Gus,

was director of research at UOP and responsible for many
of their developments as well as the hiring of several of the
great catalysts experts including Ipatieff, Haensel, and
Tropsch. During the trial, in November of 1927, an
attorney asked Egloff exactly what he knew about certain
aspects of refining. After a week the attorney pleaded for
respite but the judge ruled that Dr. Egloff was entitled to
answer the question because what he knew had a direct
bearing on the case. UOP attorneys then recognized the
value of his continued testimony and hurriedly organized a
nightly briefing to prepare Egloff for the following day.

Reprinted by permission from

Petroleum Refiner, January
1959, Copyright 1959, Gulf
Publishing Co, All Rights
Reserved

Carbon Petroleum
Dubbs
1881 1962
Reprinted by permission from

Petroleum Refiner, January

His testimony went on for some seven months and past
1959, Copyright 1959, Gulf
Easter 1928.
The St. Louis Post Dispatch paper
Publishing Co, All Rights
Reserved
editorialized after some months of testimony, "We are lost
in admiration for Dr. Egloff, but we would never be so incautious, especially if we were in a hurry, to ask
him what time it is. The briefing papers were later edited by Dr. Egloff and issued as a definitive discourse,
The Chemistry of Petroleum.

The Standard Design for Gas Oil Thermal Cracking Process with Tube and Tank
Despite the suits and conflicting thoughts on cracking liquids, a more or less standard continuous thermal
cracking design of the tube (heater) and tank (soaker drum) process evolved in the industry and persisted
through World War II. The tubular heater provided continuous heat input.
A soaking vessel replaced the narrow tubes to provide residence
time for the cracking operation to occur to some reasonable
degree of completion. Tube residence time was measured in
minutes and the soaker could provide hours of residence at
cracking conditions. The problem was that polymerization
reactions also occurred, leading to tar and coke. A chain
suspended in the vessel when it was first put on-stream removed
the coke. Pulling out the chain (with a team of mules) through the
bottom head during decoking was the first step in breaking up
coke in the soaking drum.
Thermal Reforming for Naphtha
Battery of thermal cracking stills, Type
500, Gulf Refining, Port Arthur Texas,
1925
Reprinted by permission from Petroleum Refiner, January
1959, Copyright 1959, Gulf Publishing Co, All Rights
Reserved

As thermal cracking technology advanced, the use of a milder

regime in terms of short contact time although higher
temperatures, called thermal reforming, was developed to improve
the quality of straight run gasoline. Thermally reformed naphtha
had octane numbers of 70-90 compared to 50 for virgin naphtha.
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Chapter 5 The Age of the Thermal Refinery

By 1930 most refineries had thermal reformers to upgrade gasoline quality but these lasted until the 1940s with
the introduction of catalytic reforming. All were gone by the end of the 1950s.
Thermal polymerization of the thermal light olefins
Interest in high octane blending stocks led to development of a thermal process for converting the olefinic
C3/C4 light ends to hexenes/heptenes/octenes. The light ends contained olefins and it was recognized that they
could be polymerized for production of more high-octane gasoline. A thermal gas recovery plant featuring lowpressure absorbers removed the cracked gases from the flare and recovered the light ends from the cracking
operation.
Propane and butane were mildly cracked in a furnace and then polymerized at higher pressures. The
development was a significant one in technology and it provided one more high quality blend stock. The
technology was developed in the late 1920s and persisted until the 1940s.
Tetra Ethyl Lead and Octane Number
Thermal cracking provided both volume and quality, that is, higher octane number, although that quality was not
yet so defined. Then in 1923, General Motors Chemical Company, as the manufacturer and predecessor to
Ethyl Corporation was named at that time, offered Tetra Ethyl Lead (C8H20Pb), the addition of which to
gasoline was an immediate success. It improved performance noticeably, particularly with regard to the clatter,
knock, or ping caused by pre-combustion of straight run gasoline. The first Ethyl gasoline containing Ethyl
antiknock compound was sold on February 2, 1923 from the Refiners Oil Company in Dayton, Ohio. In
September Standard Oil of Indiana signed the first contract for supplies of Tetra Ethyl Lead (TEL). Nearly all
stations soon added a gasoline pump for "Ethyl" gas.
Tetra Ethyl Lead production was a complex and dangerous process. General Motors formed a company with
Standard Oil of New Jersey for manufacture of TEL at the Bayway refinery. After a devastating explosion, the
newly formed venture, called Ethyl Corporation, moved to Baton Rouge where a refinery could provide ethylene
for TEL manufacture. Du Pont was contracted to design and operate the TEL facility. It did so for years and
upon expiration of the contract became a competitor in the production of TEL.
The advent of TEL improved gasoline quality but just how much improvement was achieved was subject to
interpretation since there was no quantitative measure of its performance. The primary desired qualities were
octane number, volatility and sulfur content. It should be noted that in addition to TEL for octane stimulation,
chemists were devising treating operations and additives to overcome odor, gum and other objectionable
qualities of the cracked gasoline. One disadvantage of TEL was toxicity. Red dye was added to distinguish
Ethyl from unleaded gasoline. And in 1926, the Surgeon General mandated a TEL limit of 3 milliliters/gallon
of finished gasoline. The beginning of the end of TEL was 1975, when the first of large service stations offered
unleaded gasoline.
In 1931 The Cooperative Fuel Research Committee published a test method for measuring octane so that the
octane number could be used as a measure of antiknock quality. The first octane number was determined by the
so-called motor method. The assignment of a measurable quality, octane number, to refinery streams led to
precision in refining economics and optimization of operations.
Now the improved quality results of more stringent operations could be measured and the cost of incremental
quality expressed as "per octane number barrel" could be determined. This led to optimization of thermal
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Chapter 5 The Age of the Thermal Refinery

cracking and thermal reforming to produce gasoline and kerosene, and quality of the mix of straight run and
cracked products jumped. With addition of TEL refiners could sell a Premium gasoline at a premium price.
Blending arose as an art and then a science, creating the two grades of gasoline at maximum profitability.
The Products From the Thermal Refinery
The essential feature of the Thermal Refinery was the quite rapid change from kerosene being the principle
product to gasoline being the principle product. This was due to the introduction automobile, the airplane, and
electricity. World War I, from April 1917 when the U.S. declared war on Germany until November 1918,
accelerated the demand for gasoline. And the three thermal processes - thermal cracking, thermal reforming,
and thermal polymerization - provided the processes for the expansion of gasoline yields. Demand for kerosene,
once the primary product, slipped until the introduction of the jet engine. In the southeast, coastal refineries
located in the tidelands and along the Mississippi River mostly supplied gasoline and kerosene markets. In
1911, the Standard Oil Group sold more gasoline than kerosene.
Up through 1924, despite the rapid introduction of various thermal cracking processes, over 80% of gasoline
sold was straight run and approximately 15% was cracked. But after the introduction of Tetra Ethyl Lead
antiknock compound in 1923, the growing emphasis on performance, and the solving of odor problems, the
percentage of cracked gasoline jumped to about 35% in 1926. By the end of the age of the Thermal Refinery in
1940, cracked gasoline contributed over 50% of the gasoline pool.
Thermal kerosene made in the thermal crackers was combined with virgin kerosene. The kerosene from some
shell still batteries had to be rerun to correct either initial or final boiling point or both.
Approximate Thermal Refinery
Yields
Light Ends 5%
Gasoline 35%
Kerosene 30%
Lubes, fuel oil, asphalt, tar 30%

The gas oil product was predominately thermally cracked as the

heaviest feed stock for conversion of gas oil to gasoline and
kerosene. Some gas oil was sold for heating. In metropolitan areas
gas oil was sold for town gas manufacture, normally done by
companies with a city franchise to make the gas.

Overall, fuel oil and asphalt was the major outlet for the bottom
15% to 20% of the barrel of crude. The consumer who provided
the big market for fuel oil over a vast area of the United States was
the railroad, with its steam engine. Fuel oil in the Midwest displaced coal as the locomotive fuel of choice and
refineries sprang up where a gasoline and kerosene market area was bisected by a major rail line. In the
southeast, there was less pressure to move fuel oil to the railroads, so coal and wood continued to tussle for that
market well into the 20th century. Diesel for the few diesel-electric locomotives was an insignificant market.
Shell stills and the earliest pipe stills both produced "tar," a stock that could be blended into residual fuel oil for
ships at the refineries located on deep water. Refiners did not process atmospheric residuum much less vacuum
resid. Asphalt was produced from asphaltic crudes, but not all crudes contain significant amounts of asphalt.
Asphalt refineries were smaller, generally located near a source of asphaltic crude, and served a relatively small
gasoline market area. Resid was not usually burned. Electric power plants burned coal in preference to resid,
for economic reasons. In fact many refineries in the east and Great Lakes region burned coal too.
If lube crude were available, lube cuts were preferably made from the pipe still and were referred to as waxy
distillate cuts. The lube cut was first chilled and passed through a canvas filter bag to remove solid wax. The
dewaxed lube cut then was subject to various treating processes, including acid and caustic treating plus clay
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Chapter 5 The Age of the Thermal Refinery

contacting. Toward the end of the 1930s a heavier lube fraction was dissolved in propane and asphaltic
compounds were precipitated, making it possible to make heavier lube fractions from resid. Not all refineries
produced lube oils. It was an expensive and small volume, albeit profitable operation. In fact, "fuel only"
refineries outnumbered lube refineries.
The Thermal Refinery Configuration and Evolution
Distillation
Over the years thermal refineries, even those without lube operations, became somewhat complex. At one time
the refinery manager or operating superintendent was expected to be his own technologist but the advent of
extensive treating operations and thermal cracking led to the addition of chemists to the refinery staff. These
"petroleum chemists" were primarily responsible for both product quality and process revisions.
The Thermal Refinery
Methane & Ethane

Other Gas Sources*

Gas Plant
Light Ends

Naphtha

Atmospheric
Column
(Pipe Still or
Series of
Shell Stills)

Propane &
Butane

Thermal
Reforming
(light
cracking)

Thermal
Polymerization

Gas*

Gasoline

Tar*

Kerosene (Distillate)

Gas Oil

Gas*

Thermal
Cracking
(heavy
cracking)

Fuel
Gas
Gas*
Tar Residue*

Gasoline
Treating

Gasoline

Kerosene
Treating

Kerosene

Kerosene
Gasoline
Town
Gas
(hydrogen
and carbon
monoxide)

Tar*
Gasification
using the
shift

Steam
Lube Oil

Lube
Treating

Fuel
Oil

Other Sources of Tar*

Asphalt Resid (Tar)
Steam and Air
Note: Disposition of gas * and tar * is not shown.

Page 5-7

Lube
Oil(s)

Treating
Asphalt
Resid

Asphalt

Refining Overview Part 2 Development of the Modern Refinery

Chapter 5 The Age of the Thermal Refinery

A refinery actually might have more than one battery of stills. These were usually combinations of pipe and
shell stills. When additional stills were added to the battery, they were usually pipe stills, which provided more
precise fractionation. Often the pipe still was the first still in the battery. And if lube fractions were cut pipe
stills were preferred. A typical still battery might have eight to ten stills and a spare was common. The pipe
stills might range from 5,000 to 25,000 barrels per day of charge capacity. Initially the pipe still had no vacuum
flasher or vacuum tower. Vacuum distillation was added in refineries about 1925 to increase distillate gas oil
recovery and improve lube fractionation. It is not clear when side stream strippers were added to correct initial
boiling point of a side stream cut on a vacuum fractionator. Piping was arranged to take any still out of
operation for cleaning and repair. In more modern shell stills, the crude was preheated in a series of exchangers,
one exchanger at the top each of the fractionators. This raised the crude temperature to almost 400F at the inlet
shell and reduced the water condenser heat load by partially condensing top vapors from each still fractionator.
In some refineries, the stills at the end of the battery could be
devoted to lube fractions. The bottoms, called tar, were directed to
fuel oil or in some cases asphalt manufacture. The temperature in
the shells ranged from 400F to about 700F.
Refineries frequently had saturate debutanizers processing field
natural gasoline and cracking coil debutanizers processing the
cracked gasoline. The debutanizer gases were sent to the refinery
gas plant. Gases from the shell and pipe stills were directed to the
gas plant for recovery of propane and butane to feed to the thermal
polymerization plant which both cracked propane/butane and
polymerized the corresponding light olefins.
The Vacuum Oil Company, Rochester
New York, late 1800s
Reprinted by permission from Oil and Gas Journal,
January 1959, Copyright 1959, PennWell Corp, All
Rights Reserved

In addition to the crude oil shell still batteries, some refineries had
rerun batteries of about three shell stills primarily for adjusting
endpoints of kerosene and in some cases some of the virgin or
cracked naphtha streams. Elimination of re-running was one
justification for pipe stills, which could make more precise cuts.

After shell stills were no longer used for crude oil, some refineries still maintained several to rerun "slop," the
oil recovered from ditches and the separators. Frequently a batch operation, they separated water overhead, then
oil overhead and discarded solids and sludge in a tar that was burned in a pit.
Thermal Crackers
The Burton batch process, developed in 1912, could not compete with later thermal processes. It is reported that
of the 1,200 Burton or Burton-Clark processes in existence in 1928, only 191 remained in 1930. However,
more advanced thermal cracking units operated until the late 1950s.
Beginning in the 1920s and by the late 1930s, most refineries had eventually added all three thermal processes:
thermal cracking of gas oil, thermal reforming of naphtha and thermal polymerization of the thermal light
olefins.
Both "thermal reforming" and "thermal cracking" units processed streams from atmospheric distillation using
batteries of stills. Cracking coils were aligned in batteries of up to ten coils like shell stills but each coil was
usually operated as a separate unit except for the light ends collection and the debutanization of naphtha.
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Chapter 5 The Age of the Thermal Refinery

A refinery might have two tube and tank batteries for gas oil cracking. The units might charge approximately
1,500 barrels per day of gas oil and had to be taken off line regularly for removal of coke from the soaking
drum. The heater was manufactured with the return bends exposed so the bends could be removed to permit
drilling out the tubes after they coked up. As late as the fifties, refineries still resounded to the noisy drilling of
cracking coil tubes.
Additionally, a refinery would have one or two batteries of thermal reformers that were coil only units with no
soaking drum to reduce residence time.
In later years, a refinery may also employ visbreaking, mild cracking of heavier gas oil to make some naphtha
and reduce viscosity of fuel oil blend stock. Severity of visbreaking was limited by avoidance of extensive
coking. As with reformers, visbreakers were coil only units.
Chemical and Clay Treating for Gasoline and Kerosene
The extent to which chemical treating was employed in a thermal refinery cannot be over emphasized. Thermal
cracking created the need for gum removal and elimination of ring compounds that impaired the smoke point.
The major emphasis on treating in a thermal refinery involved acid washing, caustic washing, doctor solution,
and hypochlorite solutions for purifying gasoline and kerosene streams to remove color, sulfur and smoke
forming ring compounds. Treating was a black art and there were no standard recipes. All refineries had an
array of "agitators" in the treating area for mixing oil with acid, or caustic or water washing. Air was often used
to help mix.
The most common chemical treatment for mercaptan sulfur in gasoline was doctor sweetening. Lead monoxide
(litharge) mixed with sodium hydroxide formed lead plumbite (Na2PbO2) and water or doctor solution. A
little sulfur was used to start the reaction. Hydrogen sulfide, if present, might be removed by use of strong
caustic before doctor treatment. A hypochlorite process was sometimes employed to oxidize sulfur but it is
more expensive. The expensive cupric oxide process was no longer utilized. Fixed bed percolation clay
treatment was sometimes used for desulfurization of straight run naphtha that were not intended for thermal
reforming. In this process of clay contacting, the clay was rather coarse and it was not necessary to filter the
fine particles from the oil. The clay was regenerated periodically in a kiln.
Kerosene was sometimes treated with doctor solution, but it was more common to use strong sulfuric acid
followed by caustic and water wash. Acid washing was intended to attack sulfur but also to remove the
aromatic smoke forming ring compounds. However, if the kerosene had a high concentration of aromatics, it
was more common, particularly in larger refineries, to use the Edeleanu liquid sulfur dioxide solvent extraction
process to remove aromatics and improve kerosene smoke point. Cupric oxide for sulfur removal was
occasionally used for kerosene. A typical treat was five pounds per barrel of cupric oxide stirred up in a tank
with a system of slow moving paddles for a day or two. Sometimes, this was followed by clay treatment. It was
usually necessary to rerun kerosene after drastic chemical treatment and in that event there was no rerun
operation on the stream as produced from the shell still.
Lube oils were referred to as "wax distillate," since they were part of the gas oil that was highly paraffinic and
waxy. Wax was removed by chilling. A variety of acid and caustic treats were employed primarily for removal
of aromatics. In some instances, the Edleaneau process was employed to remove the aromatics and minimize
the sludge formation associated with acid treating. Almost all lubes were clay contacted but in this case the clay
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Chapter 5 The Age of the Thermal Refinery

was a fine particle material and pressure filtration was required to recover oil from the solid. Clay contacting
had a marked effect on color and sheen.
These treatments resulted in a generation of acid sludge and spent caustic that had to be discarded. In addition
there were systems for elimination of sulfur using doctor solutions and hypochlorite solutions.
The chemical treatments were largely displaced in the catalytic refinery of the forties and certainly in the
modern refinery of the seventies and later. Air pollution was noticeable and objectionable but water and land
pollution were severe. The age of chemical treatment is largely overlooked but chemicals actually shared the
stage with thermal operations to produce gasoline and kerosene of suitable quality.
The Age of the Thermal Refinery Comes to a Close
The thermal refineries responded to the astounding growth in gasoline demand beginning with the
popularization of the automobile at the turn of the century. However, World War II and the need for highoctane aviation gasoline made obsolete the technology of the thermal age although many units remained in
operation for a decade or more after the war. The solution to the gasoline quality problem and the need for more
gasoline from the barrel of crude lay in the development of fluid catalytic cracking, alkylation, and platinum
catalyst reforming. The platinum catalyst reformer provided high gasoline octane rating but equally as
important, it provided hydrogen for hydrotreating that in time displaced chemicals for treating. Men such as
Vladimir Ipatieff, a Russian physical chemist who was hired by Gustav Egloff for UOP at the World Energy
Conference in Berlin in 1930, accelerated the transition from the thermal age to the catalytic age. Catalytic
processing presented the defining boundary of the new age that would differ substantially from the proceeding
Thermal Refining Age.
Summary of The Age of the Thermal Refinery - 1910 to 1940
The age of the thermal refinery can be summarized as follows for comparison with the ages before and after it.
Principal Products
Gasoline for automobile fuel and later aviation fuel was becoming increasingly important.
Kerosene for illumination was declining rapidly.
Gas oil was used for boiler fuel and town gas manufacture in cities.
High quality lubricating oils for internal combustion engines were important.
Heating oil was displacing coal for home commercial heating.
Heavy fuel oil was used for railroad steam locomotives. Diesel-electric locomotives were few.
Principal Processes
Pipe stills and shell stills were used for continuous distillation. The pipe still slowly replaced the shell
still battery.
Gas oil was thermally cracked for gasoline and kerosene.
Naphtha was thermal reformed for gasoline high in olefins with good antiknock properties.
Light ends were thermal polymerized for gasoline.
The addition of tetra ethyl lead (TEL) improved the octane number to make premium gasoline.
Chemical treating of gasoline, kerosene and lube stocks was important to remove color, sulfur and smoke
forming ring compounds.
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Chapter 5 The Age of the Thermal Refinery

Principal Problems
Chemical treating processes and wastes from chemical treating presented difficult disposal problems.
Removal of coke made in thermal operations was difficult.
Gum presented problems for the high olefinic characteristic of thermally reformed gasoline.
Internal combustion engines required high performance lubes.
A measure of motor gasoline anti-knock quality was delayed until 1930.
The former primary market for kerosene declined with no clear replacement market.
World War II increased the need for more gasoline.

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