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Petroleum Processing

The Catalytic Refinery (1940-1970)

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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.

Configuration of catalytic refinery 1940-1970. For key information see surrounding text.
Figure 11.5. The configuration of the catalytic refinery [4].

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.

Table 11.1. Historical time-line for petroleum refining processes [6].
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


[4.] F. Self, E. Ekholm, and K. Bowers, Refining Overview - Petroleum, Processes and Products, AIChE, 2000, Chapter 6. [6.] M.R. Riazi, S. Eser2, J. L. Peña Díez, and S. S. Agrawal, “Introduction” In Petroleum Refining and Natural Gas Processing, Editors: M. R. Riazi, S. Eser, J. L. Peña, S. S. Agrawal, ASTM International, West Conshohocken, PA, 2013, p.6