Hydrocarbon Processing - May 2022 - 69

History of the HPI
Flanigen as a world expert on zeolite
synthesis and the first to synthesize highsilica
Y with silica/alumina rations above
4, the first to remove aluminum from zeolite
lattices without loss of structure, and
responsible for identifying and evaluating
the myriad of samples from Union Carbide's
investigation of sedimentary zeolite
deposits in the Western U.S.109
Dr. Flanigen's
work was detailed in the Industry
Pioneers segment published in the April
issue of Hydrocarbon Processing.
In the 1950s, while working at Mobil
Oil, American chemical engineers
Charles Plank and Edward Rosinski were
researching various catalysts. During their
research, they decided to test zeolite as a
catalyst for catalytic cracking. Plank and
Rosinki's research on zeolite catalysts
showed superior activity and selectivity,
which led to dramatically higher gasoline
yields during the cracking process. According
to literature, the increased gasoil
conversions could also be obtained without
increasing gas or coke yields-two
unwanted byproducts of cracking.110,111
The two chemists
submitted their
patent-Catalytic cracking of hydrocarbons
with a crystalline zeolite catalyst
composite-to the U.S. Patent Office in
July 1960.111
The patent submission and
subsequent literature written by Plank
described the catalyst as consisting of
a finely divided crystalline aluminosilicate,
having uniform pore openings
between 6 ångströms (Å) and 15 Å, dispersed
in an inorganic oxide matrix with
a low sodium content.111,112
The technology patent was approved
on July 7, 1964. Plank and Rosinski's patent
laid the foundation for modern catalytic
cracking. Due to its molecular structure,
zeolite catalysts are extremely effective in
the reaction process-they have higher
performance at lower pressures.
Five years after Plank and Rosinski's
patent was approved, Robert Argauer and
George Landolt-the two also worked
at Mobil Oil-were the first to synthesize
high-silica zeolite, which was commercially
named Zeolite Socony Mobil-5
(ZSM-5). The two submitted the technology
for a U.S. patent in 1969. The patent
submission Crystalline zeolite ZSM-5
and method of preparing the same provided
a detailed analysis of the novel crystalline
aluminosilicate zeolite and its usefulness
in cracking and hydrocracking processes,
as well as within other refining processes
(e.g., alkylation, isomerization) and petrochemical
products production.113
Although the use of acrylonitrile was
ZSM-5
catalysts are still used in refining and petrochemical
plants around the world.
New petrochemical products/processes
enhance everyday life. Several
new petrochemical products were
discovered in the 1960s. These included
Kevlar, linear low-density polyethylene
(LLDPE) resins, a more cost-effective
process to produce acrylonitrile
and stretched polytetrafluorethylene
(PTFE), which came to be known as
Gore-Tex. With the significant expansion
in the global petrochemical industry,
Petroleum Refiner retitled the technical
publication to Hydrocarbon Processing
and Petroleum Refiner in 1961, then adopted
the name Hydrocarbon Processing
in June 1966. The publication's title-
Hydrocarbon Processing-represented
the integration of the global refining and
petrochemical industries and the technical
processes and operational know-how
that are synonymous with refinery and
petrochemicals production.
Acrylonitrile. The origins of acrylonitrile
trace back to 1893 when French
organic chemist and pharmacist Charles
Moureu was the first to synthesize acrylonitrile.
However, acrylonitrile did not find
a commercial use until the 1930s-industrial
producers used the material in applications
such as acrylic fibers for textiles
and synthetic rubber.114
extremely effective in several applications,
production was expensive and included
multistep processes. In the late 1950s, the
Standard Oil Co. (Sohio, later bp) discovered
a cheaper processing route through
selective catalytic oxidation to produce
acrylonitrile. This research effort was led
by Franklin Veatch. Veatch proposed that
converting light refinery gases (e.g., aliphatic
hydrocarbon propane) to oxygenates
could be profitable. In 1953, funding
was approved, and Veatch and his team
began research efforts. With only 6 wk left
of funding, Veatch's research team made a
vital discovery when conducting a test run
on propylene over a modified vanadium
pentoxide oxidant, resulting in the production
of acrolein-an additional oxidation
step would produce acrylic acid.114
In 1955, the Sohio research team began
testing oxidants as direct oxidation
catalysts, leading to the process of converting
propylene to acrolein in a single
catalytic reaction step-the process used
a bismuth phosphomolybdate catalyst.114
According to literature, acrylonitrile was
produced by feeding propylene, ammonia
and air over the bismuth phosphomolybdate
catalyst. The process resulted in
ammoxidation (i.e., the Sohio process),
which produced a 50% yield of acrylonitrile,
with acetonitrile and hydrogen cyanide
as coproducts.114,115
Approximately 4 yr after the start of
research, the Sohio process was commerFIG.
3. Rosinski (left) and Plank (right) demonstrate their invention of zeolite catalyst
prior to being inducted into the National Inventors Hall of Fame in 1979. Photo courtesy of
the National Inventors Hall of Fame.
Hydrocarbon Processing | MAY 2022 69

Hydrocarbon Processing - May 2022

Table of Contents for the Digital Edition of Hydrocarbon Processing - May 2022