Hydrocarbon Processing - December 2022 - 39
Catalysts
is that the trimetallic unsupported catalyst
developed by the concerned catalyst
supplier promoted excessive C-C bond
cleavage by metal components, also
known as hydrogenolysis. This metal-catalyzed
hydrogenolysis mechanism results
in high C1
and C2
hydrocarbons yields,
along with light n-paraffins and a near absence
of iso-paraffins.
Fast forward to the subsequent bidding:
this catalyst supplier decided not
to include this trimetallic catalyst in the
offered loading scheme, but returned to
a conventional Ni-Mo hydrotreating catalyst.
This implies a performance trade-off
in the supposedly high-performing trimetallic
hydrotreating catalyst. Otherwise,
the supplier would have continued to
propose it in the following cycle to gain
performance advantages in the bidding.
" There is no need to test diesel hydrotreating
catalysts. " The authors
actually heard a diesel hydrotreating catalyst
vendor say this after a refiner suggested
that pilot plant testing might be used
to better evaluate diesel hydrotreating
catalysts in the next bid process.
The vendor's reasoning was that such
a " less critical refining unit " did not require
pilot plant testing. The authors disagree
with this catalyst vendor and question
whether they will lose a bid again in
a fair process.
In contrast with hydrocracking units,
diesel hydrotreaters produce much lower
light-ends yields (gas and naphtha),
mainly from hydrotreating reactions of
sulfur, nitrogen, olefin and aromatic compounds
(see the previous section). In
diesel hydrotreating applications, hydrocracking
reactions are negligible unless
dewaxing catalysts (zeolitic-based) are
used for cloud point reduction.
Hydrotreating conversion is less than
3 wt% without dewaxing, although a decently
cut straight-run feed (e.g., from a
crude distillation column) would easily
achieve > 98 wt% diesel yield. This is one
reason the selectivity of diesel hydrotreating
catalysts is rarely discussed. A more
popular discussion topic is the optimal
ratio between Co-Mo and Ni-Mo catalysts
and how to stack them in a reactor.
It is difficult for refiners to accurately
quantify the light-ends yields in an operating
environment due to inherent flow
measurement errors. Naphtha flow is
only a tiny fraction of total product flow,
while offgas flow is notoriously inaccurate
due to varying gas composition. It
is not uncommon to see a raw mass feed
flowrate with a flow reading less than that
of the diesel product.
As discussed previously, the diesel
yield usually lies somewhere between 98
wt% and 100 wt% for most straight-run
diesel hydrotreaters, which is actually less
than the possible orifice flowmeter error
of +/- 3 wt%-5 wt%. Unsurprisingly, an
error in diesel flow measurement could
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Hydrocarbon Processing - December 2022
Table of Contents for the Digital Edition of Hydrocarbon Processing - December 2022
Hydrocarbon Processing - December 2022 - 1
Hydrocarbon Processing - December 2022 - 2
Hydrocarbon Processing - December 2022 - 3
Hydrocarbon Processing - December 2022 - 4
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Hydrocarbon Processing - December 2022 - 10A
Hydrocarbon Processing - December 2022 - 10B
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