Catalyst Hydrodeoxygenation

Hydroprocessing is a general term used for the catalytic reactions that use hydrogen to
eliminate the heteroatoms such as sulfur, nitrogen, oxygen, and metals, and also to saturate the
olefins and aromatics.

Typical hydroprocessing reactions include hydrodesulfurization (HDS)

where the sulfur is removed by breaking C-S bonds and hydrogen sulfide is formed;
hydrodenitrogenation (HDN) which

targets

the

removal of

nitrogen as

ammonia;

hydrodeoxygenation (HDO) which removes oxygen as water; and hydrodemetalization (HDM)

to remove metals such as metal sulfides.
Hydrogenation-derived renewable diesel (HDRD) production focuses on the oxygen removal from
the bio-oils/fats, which correspond to a HDO reaction, to obtain hydrocarbons in diesel fuel range
(Figure 10). HDO reactions of bio- oils/fats operate at moderate temperatures, between 300-600
C, and under high hydrogen pressure in the presence of a heterogeneous catalyst.
However, the reaction conditions such as temperature and pressure should be adjusted depending
on the feedstock. The catalysts used for HDO are in fact the same as those that are used for HDS
and HDN such as sulfided Co-Mo or Ni-Mo because the hydrogenation processes are very
similar in petroleum refineries.

Figure 10. The oxygen removal from the triglycerides (HDO reaction)

t has been shown that it is possible to produce an alternative diesel fuel (green diesel) via

hydrogenation of triglycerides, which can be also called HDRD.

Because HDRD is

characterized by a high cetane number, its preferred use is a diesel fuel additive to improve fuel
ignition. Hydroprocessing of vegetable oils such as palm oil will produce hydrocarbons in the
diesel boiling range (mainly C15

- C18

paraffins) which can act as a fuel ignition

improvers. They carried out the process at a temperature of 350-450 C and 4.8-15.2 MPa by
using a commercially available hydroprocessing catalyst such as Co-Mo and Ni-Mo

Catalyst Decarboxylation

Palladium on carbon, often referred to as Pd/C, is a form of palladium used for catalysis. It
is usually used for catalytic hydrogenations in organic chemistry. When the metal is distributed
over finely-divided carbon catalyst support, the surface area is larger and the catalyst is more
reactive. A later study demonstrate ed that for green diesel production via decarboxylation of
stearic acid over 4 wt. % Pd catalyst supported on sibunit (a new class of mesoporous carboncarbon composite materials combining advantages of chemical stability and electric
conductivity of graphite and high specific surface area and adsorpt ion capacity of active coals)

39

is possible.

This process was carried out in a semi-batch reactor with 300 mL volume at 17

o
bar helium and 300 C, using dodecane as a solvent . Under these conditions, the catalytic
decarboxylation of stearic acid resulted in n-pentadecane formation as well as n-heptadecane as
the main products. Thus, it is concluded that the product distribution in catalytic decarboxylation
of stearic acid changes depending on the type of the support and the nature of the surface
39

groups in carbon material.

Some of the tested decarboxylation reactions for conversions of fatty acids are shown in Table
Table 5. Literature summary of decarboxylation reactions of fatty acids.