The preparation of
zeolite-based bifunctional catalysts with low
noble metal loadings while maintaining optimal performance has been
studied. We have deposited 0.03 to 1.0 wt % Pt on zeolite H-USY (Si/Al
∼ 30 at./at.) using either platinum(II) tetraammine nitrate
(PTA, Pt(NH
3
)
4
(NO
3
)
2
)
or hexachloroplatinic(IV) acid (CPA, H
2
PtCl
6
·6H
2
O) and studied the nanoscale Pt loading heterogeneities
and global hydroconversion performance of the resulting Pt/Y catalysts.
Pt/Y samples prepared with PTA and a global Pt loading as low as 0.3
wt % Pt (
n
Pt
/
n
A
= 0.08 mol/mol, where n
Pt
is the number of Pt surface
sites and
n
A
is the number of acid sites)
maintained catalytic performance during
n
-heptane
(
T
= 210–350 °C,
P
=
10 bar) as well as
n
-hexadecane (
T
= 170–280 °C,
P
= 5 bar) hydroisomerization
similar to a 1.0 wt % Pt sample. For Pt/Y catalysts prepared with
CPA, a loading of 0.3 wt % Pt (
n
Pt
/
n
A
= 0.08 mol/mol) sufficed for
n
-heptane hydroisomerization, whereas a detrimental effect on
n
-hexadecane hydroisomerization was observed, in particular
undesired secondary cracking occurred to a significant extent. The
differences between PTA and CPA are explained by differences in Pt
loading per zeolite Y crystal (size ∼ 500 nm), shown from extensive
transmission electron microscopy energy-dispersive X-ray spectroscopy
experiments, whereby
crystal-based n
Pt
/
n
A
ratios could be determined. From
earlier studies, it is known that the Al content per crystal of USY
varied tremendously and that PTA preferentially is deposited on crystals
with higher Al content due to ion-exchange with zeolite protons. Here,
we show that this preferential deposition of PTA on Al-rich crystals
led to a more constant value of
n
Pt
/
n
A
ratio from one zeolite crystal to another,
which was beneficial for catalytic performance. Use of CPA led to
a large variation of Pt loading independent of Al content, giving
rise to larger variations of
n
Pt
/
n
A
ratio from crystal to crystal that negatively
affected the catalytic performance. This study thus shows the impact
of local metal loading variations at the zeolite crystal scale (nanoscale)
caused by different interactions of metal precursors with the zeolite,
which are essential to design and synthesize optimal catalysts, ...