
The Catalytic Refinery (1940-1970)
As discussed in Lessons 6 and 7, the development of catalytic processes has changed the chemistry of petroleum refining from free radical to ionic reactions. World War II provided the stimulus to urgently develop catalytic technologies that were being investigated in the late thirties. The catalytic age of refining, which could be bracketed between1940 and 1970 also brought the advent of the petrochemical industry.
Figure 11.5 shows a configuration of the catalytic refinery which resembles, to a large extent, the current day refineries focused on making high yields of gasoline. The introduction of catalytic cracking, reforming, alkylation, polymerization has revolutionized the ways of making high octane number gasoline. Development of hydrotreatment processes was also an important asset of the catalytic refinery. Hydrotreatment was essential to protect the platinum catalyst used in reforming from sulfur and as a versatile finishing process to replace the chemical treatments used in the thermal refinery to finish fuels.

One should note in Figure 11.5 that the catalytic refinery also incorporated new thermal processes such as delayed coking and visbreaking, and separation processes, such as deasphalting. Principles of chemical engineering have found great applications in the development of the catalytic refinery with particular emphasis on designing different catalytic process configurations (remember Fixed-Bed, Moving-Bed, and Fluid-Bed Catalytic Cracking), catalyst development, thermal efficiency (e.g., FCC) and product yield and selectivity. The catalytic refinery produced large quantities of LPG (for reasons discussed in Lesson 7) and witnessed the increasing demand for kerosene, now as jet fuel. The time-line for the development of refining processes shown in Table 11.1 shows the intense activity of process development, particularly during World War II.
The age of catalytic refining may be considered to have ended in the 1970s, not because new chemistry was introduced, as it happened in the transition from thermal to catalytic refinery or the development of new process concepts. The oil crises of the 1970s highlighted the significance of refinery flexibility with respect to the diversity of crude oil slates. Further, the concerns for environmental pollution by the combustion of petroleum fuels have brought emphasis on more effective finishing processes. These factors lead to the development of the modern refinery focused on processing the heavy ends of petroleum and making cleaner fuels.
Year | Process Name | Purpose | Byproducts, etc. |
---|---|---|---|
1849 | Canadian geologist Abraham Gesner distills kerosine from crude oil | ||
1859 | An oil refinery is built in Baku (Azerbaijan) | ||
1860-1861 |
Oil refineries are built near Oil Creek, Pennsylvania; Petrolia, Ontario, Canada; and Union County, Arkansas |
||
1862 | Atmosphere distillation | Produce kerosine | Naphtha, tar, etc. |
1870 | Vacuum distillation | Lubricants (original) cracking feedstocks (1930s) |
Asphalt, residual coker feedstocks |
1913 | Thermal Cracking | Increase gasoline |
Residual, bunker fuel |
1916 | Sweetening | Reduce sulfur and odor | Sulfur |
1930 | Thermal reforming | Improve octane number | Residual |
1932 | Hydrogenation | Remove sulfur | Sulfur |
1932 | Coking | Produce gasoline base stocks |
Coke |
1933 | Solvent extraction | Improve lubricant viscosity index | Aromatics |
1935 | Solvent dewaxing | Improve pour point | Waxes |
1935 | Catalyst polymerization | Improve gasoline yield and octane number | Petrochemical feedstocks |
1937 | Catalytic cracking | Higher octane gasoline | Petrochemical feedstocks |
1939 | Visbreaking | Reduce viscosity | Increased distillate, tar |
1940 | Alkylation | Increase gasoline octane and yield | High-octane aviation gasoline |
1940 | Isomerization | Produce alkylation feedstock | Naphtha |
1942 | Fluid catalytic cracking | Increase gasoline yield and octane | Petrochemical feedstocks |
1950 | Deasphalting | Increase cracking feedstock | Asphalt |
1952 | Catalytic reforming | Convert low-quality naphtha | Aromatic |
1954 | Hydrodesulfurization | Remove sulfur | Sulfur |
1956 | Inhibitor sweetening | Remove mercaptan | Disulfides |
1957 | Catalytic isomerization | Convert to molecules with high octane number | Alkylation feedstocks |
1960 | Hydrocracking | Improve quality and reduce sulfur | Alkylation feedstocks |
1974 | Catalytic dewaxing | Improve pour point | Wax |
1975 | Residual hydrocracking | Increase gasoline yield from residual | Heavy residuals |
1975 | Catalytic converter | The phaseout of tetraethyl lead begins | Cleaner air |
1990s | SCANfining (Exxon), OCTGAIN (Mobil), Prime G (Axens), and S Zorb (Phillips) | Reformulated gasoline and low-sulfur diesel | Low sulfur fuel |
2000 | Deep or ultra-deep desulfurization (ULSD) | Decrease sulfur level in diesel (2 ppm0 | Sulfur |