1.

Production of Low-Sulfur Diesel Fuel

(Matthew J. Quale, Mobil Technology Company, January 2000)

There is a trend in recent environmental legislation to lower sulfur specifications in both gasoline
and diesel fuels. You work for a refinery in the Delaware Valley that anticipates a new diesel
specification requiring an order of magnitude lower sulfur than currently allowed. In fact,
legislation is already in the works in Europe to lower the allowable sulfur to this new level by the
year 2005. To achieve these low sulfur levels, you are to design a new catalytic
hydrodesulfurization (HDS) system. This type of reactor has been in use in industry for a long
time, but never for such severe service.

This unit will require just two feeds: a liquid feed blend from your refinery, and hydrogen. Since
your refinery does not have a reforming unit (common hydrogen source within a refinery) or a
hydrogen plant, you will have to buy the necessary hydrogen from a third party. Fortunately, a
group similar to yours (1998/1999 Penn Senior Design Group – Khandker et al., 1999) recently
designed a new hydrogen plant for the Delaware Valley that should be on-stream shortly before
your unit and they are looking for new long-term supply agreements. Use the conclusions from
their published report for information on the hydrogen purity and price. (I would recommend
researching current contract hydrogen prices to ensure they are charging a reasonable price,
however.)

Your R&D department has done substantial pilot plant work on this new process and has
determined the following correlations to assist you in designing the HDS reactor. You also have
processing data available from an older HDS unit within your company to use as a baseline.

Processing Conditions

A common value to track while designing a HDS unit is the percent hydrodesulfurization (%HDS):

Different catalysts have different intrinsic activities, aging rates, and processing
abilities/robustness. For your particular feedstock, the R&D department found the following
correlations based on a reference catalyst. Terms denoted with a “0” are the baseline data provided
in Table 2. The start-of-cycle (SOC) temperature is given by
The values for constants (A – F) and the base and proposed operating parameters are given in the
following tables. Please note that the equation and constants are Mobil Corporation internal
numbers and should be cited as such.

The circulation and pressure values for the proposed operation are given as minimums to achieve
the necessary product specifications. Increasing these values will improve the catalyst life, but
result in higher capital and operating costs. It is left to you to determine the optimum values from
an economic standpoint. To determine the catalyst cycle length, take 750°F as the maximum
average bed temperature because higher values will produce product which has a color greater
than ASTM 2.0 (the current spec).

Feed and catalyst information along with a brief overview of catalytic hydroprocessing (HDS in
particular) will be presented to your group prior to beginning the project.

References

Grancher, P., Hydrocarbon Processing, July, 1978, p. 155; September 1978, p. 257.

Khandker, D., A. Lam, and M. Molloy, “Hydrogen Production Using Steam Reforming and Water
Gas Shift Technologies,” University of Pennsylvania, Towne Library (1999).

Satterfield, C. N., Heterogeneous Catalysis In Practice, 1980; Section 9.8, p. 259.

U.S. Patent 5,011,593 to Mobil Oil Corporation

U.S. Patent 5,474,670 to Exxon Research and Engineering

U.S. Patent 5,454,933 to Exxon Research and Engineering