Brief History
Hydrotreating has its origin in the hydrogenation of finely powdered, bituminous
coal to liquid hydrocarbons, accomplished by Berthelot in 1869 with a nascent
hydrogen source, hydriodic acid (Berthelot 1869). In 1897, Sabatier and
Senderens published their discovery that unsaturated hydrocarbons could be
hydrogenated in the vapor phase over a finely powdered, reduced nickel catalyst
(Sabatier and Senderens 1897). Shortly after the turn of the century, Ipatieff
extended the range of feasible hydrogenation reactions by the introduction of
elevated hydrogen pressures (Ipatieff et al. 1900). At the time, the progress of the
automobile industry was expected to entail a considerable increase in the consumption of gasoline. This led to the experimental work by Bergius, started in
1910 in Hanover, Germany, who sought to produce gasoline by cracking heavy
oils and oil residues as well as converting coal to liquid fuels. He realized that to
remedy the inferior quality of the unsaturated gasoline so produced, the hydrogen
removed mostly in the form of methane during the cracking operation has to be
replaced by addition of fresh hydrogen. Thus, formation of coke was avoided and
the gasoline produced was of a more saturated character. Bergius also noted that
the sulfur contained in the oils was eliminated for the most part as hydrogen
sulfide. Ferric oxide was used in the Bergius process to remove the sulfur.
Actually, the ferric oxide and sulfides formed in the process acted as catalysts,
though the activity was very poor. The first plant for hydrogenation of brown coal
was put on stream in Leuna, Germany, in 1927 (Stranges 1984). The plant utilized
unsupported molybdenum and tungsten sulfides (TMSs) to hydrogenate brown
coal. The first TMS catalysts supported on activated γ-alumina were developed
and in use during the early 1940s by I.G. Farbenindustrie AG/Badische Anilinund Soda-Fabrik (BASF) in Ludwigshafen, Germany. Metal shortages while in
wartime motivated the idea to disperse a relatively smaller quantity of metals on
an activated alumina support (Wu and Storch 1968). Among the first such
catalysts utilized industrially were catalysts 7,846 (NiMo) and 8,376 (NiW)
(Weisser and Landa 1973; Pier 1949). The past large-scale industrial development
of hydrogenation in Europe, particularly in Germany, was due entirely to military
considerations. Germany used hydrogenation extensively during World War II to
produce gasoline: 3.5 million tons were produced in 1944. The first commercial
hydrorefining installation in the United States was at the Standard Oil Company of
Louisiana in Baton Rouge in the 1930s. WWII plants were developed by Humble
Oil and Refining Company and Shell Development Company, though there was
considerably less dependence on hydrogenation as a source of gasoline. Even
though hydrogenation has been of interest to the petroleum industry for many
years, hydrogen-consuming processes were seldom used industrially due to the
lack of low-cost hydrogen. This limitation was relieved in the early 1950s upon
the advent of catalytic reforming, making by-product hydrogen more readily
available, thus motivating an extensive and increased interest in processes that
utilized such hydrogen to upgrade petroleum stocks. As a result of the enormous
Hydrotreating in Petroleum Processing
365
Hydrotreating has its origin in the hydrogenation of finely powdered, bituminous
coal to liquid hydrocarbons, accomplished by Berthelot in 1869 with a nascent
hydrogen source, hydriodic acid (Berthelot 1869). In 1897, Sabatier and
Senderens published their discovery that unsaturated hydrocarbons could be
hydrogenated in the vapor phase over a finely powdered, reduced nickel catalyst
(Sabatier and Senderens 1897). Shortly after the turn of the century, Ipatieff
extended the range of feasible hydrogenation reactions by the introduction of
elevated hydrogen pressures (Ipatieff et al. 1900). At the time, the progress of the
automobile industry was expected to entail a considerable increase in the consumption of gasoline. This led to the experimental work by Bergius, started in
1910 in Hanover, Germany, who sought to produce gasoline by cracking heavy
oils and oil residues as well as converting coal to liquid fuels. He realized that to
remedy the inferior quality of the unsaturated gasoline so produced, the hydrogen
removed mostly in the form of methane during the cracking operation has to be
replaced by addition of fresh hydrogen. Thus, formation of coke was avoided and
the gasoline produced was of a more saturated character. Bergius also noted that
the sulfur contained in the oils was eliminated for the most part as hydrogen
sulfide. Ferric oxide was used in the Bergius process to remove the sulfur.
Actually, the ferric oxide and sulfides formed in the process acted as catalysts,
though the activity was very poor. The first plant for hydrogenation of brown coal
was put on stream in Leuna, Germany, in 1927 (Stranges 1984). The plant utilized
unsupported molybdenum and tungsten sulfides (TMSs) to hydrogenate brown
coal. The first TMS catalysts supported on activated γ-alumina were developed
and in use during the early 1940s by I.G. Farbenindustrie AG/Badische Anilinund Soda-Fabrik (BASF) in Ludwigshafen, Germany. Metal shortages while in
wartime motivated the idea to disperse a relatively smaller quantity of metals on
an activated alumina support (Wu and Storch 1968). Among the first such
catalysts utilized industrially were catalysts 7,846 (NiMo) and 8,376 (NiW)
(Weisser and Landa 1973; Pier 1949). The past large-scale industrial development
of hydrogenation in Europe, particularly in Germany, was due entirely to military
considerations. Germany used hydrogenation extensively during World War II to
produce gasoline: 3.5 million tons were produced in 1944. The first commercial
hydrorefining installation in the United States was at the Standard Oil Company of
Louisiana in Baton Rouge in the 1930s. WWII plants were developed by Humble
Oil and Refining Company and Shell Development Company, though there was
considerably less dependence on hydrogenation as a source of gasoline. Even
though hydrogenation has been of interest to the petroleum industry for many
years, hydrogen-consuming processes were seldom used industrially due to the
lack of low-cost hydrogen. This limitation was relieved in the early 1950s upon
the advent of catalytic reforming, making by-product hydrogen more readily
available, thus motivating an extensive and increased interest in processes that
utilized such hydrogen to upgrade petroleum stocks. As a result of the enormous
Hydrotreating in Petroleum Processing
365