nature catalysis

Article https://doi.org/10.1038/s41929-023-00913-8

Operando magnetic resonance imaging

of product distributions within the pores
of catalyst pellets during Fischer–Tropsch
synthesis

Received: 6 June 2022 Qingyuan Zheng1, Jack Williams1, Léonard R. van Thiel1, Scott V. Elgersma1,
Mick D. Mantle1, Andrew J. Sederman    1, Timothy A. Baart    2,
Accepted: 5 January 2023
G. Leendert Bezemer    2, Constant M. Guédon    2 & Lynn F. Gladden    1 
Published online: xx xx xxxx

Check for updates The optimization of a heterogeneous catalytic process requires

characterization of the catalyst at industrially relevant conditions and
length scales. Here we use magnetic resonance imaging to gain insight into
the Fischer–Tropsch synthesis occurring in a pilot-scale fixed-bed reactor
operating at 220 °C and 37 bar, for three H2/CO feed ratios. The molecular
diffusion and carbon number of the hydrocarbon products are spatially
resolved within both the reactor and individual 1 wt% Ru/TiO2 catalyst
pellets. These data highlight the importance of mass transfer, in addition
to the nanoscale catalyst activity, on catalyst performance. In particular,
a start-up time of up to three weeks is required for the steady state to be
achieved in the catalyst pores. Further, the average carbon number
present in the pores can be as much as double that in the product wax.
The operando characterization of water and oxygenates present in the pores
is also achieved. The presence of a water-rich liquid at the pore surface
is confirmed.

In heterogeneous catalysis, the catalytic process is directly affected
by the physical structure and chemical formulation of the catalyst,
the intrinsic chemical kinetics and mass transfer characteristics of
the reaction and the internal structure and operating conditions of
the reactor. It therefore follows that to design more effective cata-
lytic processes, greater understanding of what is occurring inside
the catalyst pellet and at the length scale of the reactor itself during
process operation is required. Operando imaging techniques with
chemical resolution have previously been applied to catalytic reac-
tors; in particular, X-ray1,2, Raman3,4, ultraviolet3, infrared4,5 and nuclear
magnetic resonance (NMR)6,7 spectroscopies have been used. Reviews
of operando studies of catalysis have been reported8,9. These studies
predominantly focus on the nature of the chemistry of the active site
and the intrinsic catalytic activity of the catalytic material. Among
these techniques, magnetic resonance, including NMR and magnetic
resonance imaging (MRI), is of particular interest since it can probe
optically opaque systems directly and can measure multiple properties,
including molecular diffusion10, flow fields11 and temperature12 within
the reactor. To date, MRI studies have been limited by insufficient spa-
tial resolution to differentiate species inside (intra-pellet) and outside
(inter-pellet) the catalyst pellets, and by the need to achieve sufficient
spectral resolution such that species of interest can be differentiated
based on their chemical shifts in the acquired spectra. Examples in
which chemical resolution has been achieved within a single pellet
include imaging of propene hydrogenation within a Pt/Al2O3 pellet13
and the esterification reaction of propionic acid and 1-butanol within

1
Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK. 2Shell Global Solutions International B.V.,
Amsterdam, Netherlands.  e-mail: lfg1@cam.ac.uk

Nature Catalysis
Article https://doi.org/10.1038/s41929-023-00913-8

a Gas feed lines e

0.08

TI 1 2 FR = 2
r.f. coil FR = 1
FR = 0.5

Mole fraction
Gradient set
control

control

control
Flow

Flow

Flow
TI
Cooling
jacket

3 GC 0
0 20 40 60 80 100
Carbon number NC
4 5 PC 6
CO

N2
H2

f
Wax products Water/light products
–4
collection vessel collection vessel

ln (mole fraction)
α = 0.94
b 40 c 100 d
–5
2.0
Outlet H2/CO
30 95
α = 0.93
SC5+ (%)
XCO (%)

20 90
1.0
–6
10 85 α = 0.88
0.5

0 80 0 30 35 40 45 50
2 1 0.5 2 2 1 0.5 2 2 1 0.5 2
Carbon number NC
FR FR FR

Fig. 1 | Schematic of the reactor and reaction data. a, Schematic of the
pilot-scale FT reactor rig: 1, fixed-bed tubular reactor; 2, NMR spectrometer;
3, gas/liquid separator; 4, storage of heavy hydrocarbons; 5, storage of light
hydrocarbons and water; and 6, wet gas flow meter. The parts of the rig equipped
with trace heating are highlighted in red. TI and PC denote temperature indicator
and pressure controller, respectively. r.f., radio frequency. b, CO conversion (XCO)
at each feed ratio (FR). c, The selectivity (S) to C5+ species. d, The H2/CO ratio at
the reactor outlet. e, Carbon number distributions of the wax products collected
from the reactor outlet. f, Anderson–Schulz–Flory plots for the outlet wax
products with NC in the range 30–50. The chain growth probability α obtained for
each feed ratio is shown. For NC < 30, some gas-phase products have been formed
and therefore the wax (liquid) product data in e will not reflect the total number
of species (gas and liquid) of that carbon number produced during the reaction
(as predicted by the Anderson–Schulz–Flory model); hence, these data are not
included in the analysis.

a hydrogel bead14. However, the use of chemical shift methods in study-
ing complex polymerization reactions such as the oligomerization of
light olefins15 and Fischer–Tropsch (FT) synthesis16 is limited because
the reaction products consist of species from the same homologous
series and therefore their spectral resonances have similar chemical
shifts; this problem is made even more challenging because of the
spectral line broadening present when species are confined within the
pores of an oxide-based catalyst.
The FT reaction is the central part of processes that pro-
duce synthetic fuels and chemicals from resources such as natu-
ral gas17, biomass 18 and carbon dioxide 19. The low temperature
operation of the FT reaction converts carbon monoxide and hydro-
gen to primarily n-alkanes that have broad carbon number (NC)
distributions16:
nCO + (2n + 1) H2 → Cn H2n+2 + nH2 O.
The FT reaction is a particularly challenging reaction to under-
stand. Much attention has necessarily focused on the intrinsic activity
and selectivity of the catalyst. However, to optimize a real catalyst,
often in the form of millimetre-scale pellets, the catalyst conversion
will be influenced by more than the intrinsic reaction kinetics alone.
Common questions that arise in studying FT include the following:
How is intrinsic catalyst performance modified by including the active
sites inside a catalyst pellet20,21? Water is formed during the reaction;
in what phase is water present and how does it exist within the pore
space20,22? Further, design of reaction operating conditions will often
be achieved through numerical modelling or simulation, which relies
on assumptions of the product distribution formed inside the catalyst
pores; such information has not yet been made under true operando
conditions (that is, employing millimetre-scale FT catalyst pellets
operating under industrially relevant conditions).
In this work, magnetic resonance techniques are applied to char-
acterize the FT reaction occurring in a pilot-scale fixed-bed reactor.
The present work reports one-dimensional (1D), two-dimensional
(2D) and three-dimensional (3D) imaging of the distribution of liquid
products within the reactor. Spatial resolution of the hydrocarbon
chain length is achieved using a recently developed approach in which
spatial maps of the distributions of molecular diffusion coefficients,
D, of hydrocarbon molecules present inside the catalyst pellets are
(1) measured, and are then transformed to the carbon number distri-
butions characterizing those species23,24. Consistency with 2D NMR
spectroscopy data is confirmed. The distributions of D were measured
using spatially resolved pulsed field gradient NMR. Spatial resolution is
achieved such that molecular diffusion and hence hydrocarbon chain
length can be discriminated inside and outside of the catalyst pellets.
While this paper focuses on the ability of MRI to monitor the evolution
of carbon number distribution in real time, spectroscopic data are also
shown to characterize the presence of water and oxygenates inside
the pores.

Nature Catalysis
Article
Results
Fischer–Tropsch reaction
The FT reaction study was carried out in a pilot-scale reactor rig
designed to operate up to 250 °C and 51 bar. The reactor body is con-
structed of silicon nitride (Si3N4), a non-magnetic ceramic material,
and has an inner diameter of 20 mm. The reactor set-up inside the mag-
netic resonance magnet is shown in Fig. 1a. The reactor was placed into
the magnet of the NMR spectrometer with the catalyst bed located in
the centre of the radio frequency (r.f.) coil, where the NMR signal was
acquired. The catalyst is a 1 wt% Ru/TiO2 extrudate of diameter 2 mm
and length 5 mm. The catalyst pellets were packed into three layers in
the reactor, with the height of each catalyst layer being ~3 mm. In total,
2.7 g catalyst was used. The three catalyst layers were separated by
~10-mm-thick layers of non-porous, inert silicon carbide (SiC) particles
of 0.3 mm in diameter to achieve isothermal operating conditions.
More details on the catalyst and the reactor set-up are described in
the Methods.
The reaction was started at a H2/CO molar feed ratio of 2 and then
reduced to a feed ratio of 1 and then 0.5. The H2/CO ratio was adjusted
by changing the partial pressure of H2 while the partial pressure of
CO was maintained at 10.3 bar. After the measurements at feed ratio
0.5, the feed ratio was reset to 2 to check the stability of the catalyst.
Figure 1b,c confirms that the catalytic conversion occurring in the
pilot-scale reactor behaves as expected. In particular, CO conver-
sion (Fig. 1b) decreases whereas C5+ selectivity (Fig. 1c) increases with
decreasing feed ratio, consistent with the literature25–27. The data shown
in Fig. 1d confirm that when the reactor is operating close to the stoi-
chiometric ratio of ~2.1 (this number depends on the exact product
distribution), the H2/CO ratio remains constant along the length of
the reactor (that is, the outlet H2/CO ratio is equal to the inlet H2/CO
ratio for a feed ratio of 2). As the feed ratio decreases from the stoi-
chiometric ratio, the H2/CO ratio at the exit decreases from the feed
condition. Finally, the gas chromatography (GC) analysis of the waxes
(liquid hydrocarbon products) collected at the exit from the reactor
confirms that the carbon number distributions (Fig. 1e) of the waxes
become heavier and broader as the feed ratio decreases with a larger
chain growth probability at a lower feed ratio (Fig. 1f). These data are
consistent with the Anderson–Schulz–Flory model16,28.
Imaging of liquid accumulation within the reactor
Figure 2 shows 3D MRI 1H intensity images throughout the reactor. The
1
H signal intensity increases with an increase in the number of 1H species
present within each image voxel and hence reflects the distribution of
liquid products within the reactor. The three catalyst layers are clearly
identified, as is the presence of liquid product in the inert packing, with
substantial accumulation of product towards the bottom of the bed.
Figure 3a shows four 2D 1H intensity images acquired from layer 1
of the catalyst bed during the reaction start-up at a feed ratio of 2. Up
to a time-on-stream (TOS) of ~51 h, signal intensity is associated with
liquid-phase 1H-containing species from inside the catalyst pellets only.
After this time, a further increase in signal intensity is associated with
the inter-pellet liquid only (Supplementary Fig. 1). Figure 3b shows
a time series of the total integrated signal intensity acquired from
layer 1 over the first 200 h of reactor operation. Once the saturation
of the pore space with liquid is complete, the liquid uptake in the layer
increases more slowly up to TOS = 150 h, after which the liquid content
in this section of the reactor plateaus. Since signal is seen only inside
the pellets up to TOS = 51 h, it is possible to use this image to produce a
mask (Supplementary Fig. 2), which is then used to identify pixels that
are unambiguously associated with the signal from the liquid product
inside the catalyst pellets (that is, from the intra-pellet space). Analysis
of only the intra-pellet data is presented here.
The average diffusion coefficient of the intra-pellet liquid in layer
1 is plotted as a function of TOS in Fig. 3c, along with the average carbon
number, NC, calculated from these data (Methods). Figure 3d shows
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
Inert packing
y Catalyst layer 1
x
z
1.0
Inert packing
Catalyst layer 2
Intensity (a.u.)
Inert packing
Catalyst layer 3
Inert packing
0.1
Glass wool
Flow
Fig. 2 | Imaging catalyst bed structure and liquid distribution within the
reactor. The 3D 1H intensity image of the reactor acquired at TOS = 400 h and a
H2/CO feed ratio of 2. The field-of-view = 25(x) × 25(y) × 80(z) mm3 and the spatial
resolution = 195(x) × 195(y) × 313(z) µm3. The intensities were normalized to the
maximum intensity of the image.
the CH4 and C5+ selectivity as measured by GC on the exit stream of the
reactor. The data of Fig. 3b,d show that while the GC might indicate
steady-state behaviour at a TOS of ~51 h, coinciding with the complete
pore filling, the intra-pellet product distribution continues to change
until at least TOS = 150 h, when liquid saturation of the entire catalyst
layer is achieved. Further, the magnetic resonance data of Fig. 3c reveal
that changes in liquid composition (characterized by NC) in the pores,
as a result of mass transfer processes, are such that the achievement
of a steady state in product composition within the pores requires
TOS > 500 h. Similar timescales for reaching the steady state are
observed for the other catalyst layers. This suggests the reaction should
be operated for at least two to three weeks to stabilize before taking
heavy wax samples for characterization and is consistent with the work
of Pinard et al.29, who reported variations in wax compositions up to
21 days after reactor start-up. This observation has important implica-
tions for how catalyst screening studies are performed. Finally, Fig. 3e
combines data from Fig. 3b–d to show how NCand C5+ selectivity change
as a function of pore saturation during start-up. The average carbon
number inside the catalyst pores decreases strongly as the liquid satu-
ration of the pore space increases, thereby showing the potential for
controlling product selectivity through controlling the level of pore
saturation of the catalyst. The negative effect of pore saturation on the
selectivity to heavy products can be attributed to the increasing extent
of the diffusion limitation of CO and H2 as the pores are increasingly
saturated with wax. At the reaction conditions used, this leads to an
increase in H2/CO ratio towards the centre of the catalyst pellet20,30.
Spatially resolving molecular diffusivities and carbon
numbers
The 2D masked images showing the average diffusion coefficient, D ,
of intra-pellet liquid are presented in Fig. 4. For each feed ratio, the
Article https://doi.org/10.1038/s41929-023-00913-8

a b 1.2
TOS = 4.8 h 22.3 h 34.0 h 50.9 h
1.0

Intensity (a.u.)
0.8
Layer
0.6 saturation
Pore
0.4 saturation
0.2

0
0 Intensity (a.u.) 1 0 50 100 150 200
TOS (h)

c 8 55 d 6 94 e 91.5
50
7 50 5 93
D (10–10 m2 s–1)

6 4 92 91.0 45
45

SCH4 (%)

SC5+ (%)
SC5+ (%)
5 3 91

NC

NC
40
40
4 2 90 90.5
35
3 35 1 89

2 30 0 88 90.0 30
0 100 200 300 400 500 600 0 50 100 150 200 250 300 0.2 0.4 0.6 0.8 1.0

TOS (h) TOS (h) Pore saturation

Fig. 3 | Effect of pore filling and mass transfer processes on catalyst
selectivity. a, The 2D 1H intensity images of catalyst layer 1 acquired during
reaction start-up at a H2/CO feed ratio of 2 showing the filling of catalyst pores by
liquid products (field-of-view = 22(x) × 22(y) mm2, slice thickness = 3 mm and
spatial resolution = 172(x) × 172(y) μm2). The signal intensity of each image was
normalized to the maximum intensity of the image acquired at TOS = 50.9 h.
b, Total signal intensity of catalyst layer 1 showing the liquid accumulation in
pores and in the inter-pellet space of the catalyst layer. The signal intensities were
normalized to that acquired at TOS = 150 h. c, Average diffusion coefficient and
the corresponding carbon number of the intra-pellet liquid in catalyst layer 1
measured during the reaction start-up. The standard errors of D and NC are
estimated as 0.02 × 10−10 m2 s−1 and 0.1, respectively, using the results acquired at
TOS > 500 h for six repeat measurements. d, The CH4 and C5+ selectivity (S)
measured by GC during start-up. To highlight the initial variation, the data up to
TOS = 300 h are shown; the data at TOS > 300 h remain stable. e, Correlation
between the extent of pore saturation and catalyst selectivity.

FR = 2 FR = 1 FR = 0.5 molecular diffusion coefficient decreases down the bed, as the reaction
z
proceeds. The values of D for a given catalyst layer decrease with
y
decreasing feed ratio. Heterogeneity in the D distribution is observed
x throughout the catalyst layers and also within individual catalyst pel-
lets for all catalyst layers and feed ratios. While the present study
10
focuses on the intra-pellet liquid, the diffusion distribution of the
D (10–10 m2 s–1)

8
inter-pellet liquid was also analysed. As expected, the diffusion coef-
6 ficients of molecules in the inter-pellet space extend to larger values
4
than are found in the intra-pellet space due to the absence of tortuos-
ity constraints. The distributions of molecular diffusivity measured at
2
individual pixels in Fig. 4 were then converted to carbon number (NC)
1
distributions. The 2D maps of average carbon number, NC, are shown
in Fig. 5a. Heterogeneity in the product distribution is seen across the
Intensity (a.u.)

0
Fig. 4 | 2D maps of the average diffusion coefficient of intra-pellet products.
At each image pixel, a distribution of molecular diffusion coefficient, D, was
obtained using the spatially resolved pulsed field gradient NMR experiment,
from which the average diffusion coefficient was calculated. The spatial
resolution is 172(x) × 344(y) μm2; all other imaging parameters are the same as
stated for Fig. 3a. To improve visualization, the D maps were first interpolated to
1,024 × 1,024 matrices and then superimposed on the intensity images of the
catalyst layers. In this way, the D values are represented by the colour map, while
the brightness of a pixel indicates local signal intensity. In the D maps, some
pixels at the edge of the pellets are subject to large error and therefore not shown
(error analysis in Methods). The rows from top to bottom show the results for
catalyst layers 1–3, and the columns show the results for different feed ratio (FR)
values. The D values have standard errors of 0.20 × 10−10 m2 s−1 as estimated using
three repeat measurements.
bed. Such heterogeneity at the top of the bed is likely due to the mald-
istribution of liquid accumulation at the entrance of the reactor
(Supplementary Fig. 3). Heterogeneity in NC is also seen within
individual catalyst pellets. The probability density functions of NC
obtained from the NC maps in Fig. 5a are shown in Fig. 5b. As expected
from the data shown in Fig. 5a, for all three catalyst layers, the probabil-
ity density functions of NC shift towards larger NC with decreasing
feed ratio25,27. Figure 5b highlights differences in catalyst behaviour
along the length of the reactor for the different feed ratios. For exam-
ple, the feed ratio of 2 shows little change in the product distribution
formed within the catalyst pellets down the reactor. However, as the
feed ratio decreases, a shift to heavier products as reaction proceeds
down the bed is observed. This is explained by the decrease of the
H2/CO ratio down the reactor (Fig. 1d), which leads to heavier products
being produced in the lower part of the reactor. In addition to the effect
of the H2/CO ratio, the enhanced readsorption of olefins20 and higher
water partial pressure31 in the lower regions of the reactor are also likely
to contribute to the increasing average carbon number down the reac-
tor. Figure 5b also shows broadening of the NC distributions as the feed
ratio decreases. For completeness, the NC determined by diffusion was
validated by comparing the results with those measured using an

Nature Catalysis
Article
a FR = 2 FR = 1
z y
x
80
70
60
NC
50
40
30
1 0.1
Intensity (a.u.)
0
Fig. 5 | Average carbon numbers of intra-pellet products. a, The 2D maps of NC
of the intra-pellet products. For each pixel, a carbon number distribution was
obtained and NC was calculated. The resolution, display and interpretation of the
images are the same as in Fig. 4. The rows from top to bottom show the results for
catalyst layers 1–3. b, Histograms of the NC values shown in the images in a.
independent (not spatially resolved) method based on 2D NMR
correlated spectroscopy (COSY)32. Good agreement is obtained
between the two methods to within experimental error; the NC of the
whole catalyst bed is consistent with the average values of NC obtained
from the three catalyst layers. The 2D COSY data are reported in
Supplementary Fig. 4.
Figure 6a shows an expanded image of the region identified in
Fig. 5a to highlight the variation of carbon number within a single cata-
lyst pellet. The probability distribution functions of the NC obtained
from the catalyst pellet highlighted in Fig. 6a are presented in Fig. 6b.
The probability distribution functions of NC in the individual pellet
show similar variation with feed ratio to that observed for the entire
catalyst layer (Fig. 5b). This confirms that a heterogeneity of reaction
occurs at a length scale smaller than the size of individual pellets.
Similar data from a second pellet are shown in Supplementary Fig. 5.
The 2D images shown in Figs. 4–6 represent the catalyst behaviour
averaged over a 3 mm slice thickness along the length of the reactor
(Methods). The level of information obtained and the quality of the
data are further demonstrated by Fig. 6c and Supplementary Fig. 6, in
which the data from a single pixel are plotted. As expected, the carbon
number distribution of liquid from the selected pixel becomes heavier
and broader as feed ratio decreases.
Figures 4–6 show that it is now possible to measure the molecular
mobility directly and hence estimate the carbon number of the prod-
ucts within the catalyst pellets during the FT reaction. Figure 7 explores
further the importance of understanding product distributions in
catalyst pellets and how the insights provided by MRI yield information
that provides valuable new data on which to base numerical models of
FT catalysis in the reactor environment. Figure 7a highlights the
difference in wax (that is, hydrocarbon mixture) composition inside
the catalyst pellets and in the collected wax at the reactor exit. Measure-
ments of the intra-pellet NC are plotted, along with the results of the
collected wax as a function of H2/CO feed ratio. These data confirm that
an NC of 28, which is commonly used in numerical modelling33,34 to
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
FR = 0.5 b
0.3
FR = 2
FR = 1
0.2 FR = 0.5
0.1
Probability distribution function
0.4
Flow direction
0.3
0.2
0.3
0.2
0.1
0
30 40 50 60 70
NC
The NC values have standard errors of ~1 as estimated using three repeat
measurements. The grey box on the image for layer 3 acquired at feed ratio 0.5
identifies the local region from which the single pellet analysis shown in Fig. 6 is
performed.
characterize the wax formed within the catalyst pores, might seem
appropriate based on the collected wax data, but the wax actually
present in the pores can differ by up to 100%. This has obvious implica-
tions for understanding the reaction conditions and modelling the
reaction. Importantly, the concentration of the reactants dissolved in
the liquid wax product, determined by their solubility and diffusion
coefficients within the wax, is a function of the NC of the wax.
Figure 7b,c shows diffusivity and solubility data estimated for H2 and
CO using waxes with an NC in the range 20–80. The molecular mobility
(characterized by diffusion coefficient) and solubility (characterized
by Henry’s law constant35) of the two gases in the waxes vary notably
as a function of carbon number. In particular, using n-C28 as the repre-
sentative wax in the pore space of the catalyst overestimates diffusivi-
ties and the Henry’s law constants considerably. The magnitude of the
differences between what is estimated based on exit composition rela-
tive to actual wax composition within the pores will lead to substantial
errors, which are summarized as follows. Using n-C28 as the solvent
overestimates the diffusivities of H2 and CO by 7–18% and 11–33%,
respectively, with the error becoming larger at lower feed ratios, when
heavier products are produced. As a result, the extent of the diffusion
limitation of H2 and CO within the pellets will be underestimated to an
increasing extent as feed ratio decreases. Importantly, the extent to
which the CO diffusivity is overestimated is greater than that for H2,
which will change the H2/CO ratio present in the catalyst pellets from
that expected based on the feed condition; this will affect catalyst
performance20,30. For the solubility data in Fig. 7c, the Henry’s law
constants calculated using an NC of 28 overestimate the true values
for H2 and CO by 15–98% and 13–80%, respectively. This suggests that
the actual mole fractions of H2 and CO in pores are respectively 1.2–2
times and 1.1–1.8 times larger than those commonly estimated, which
will influence the reaction rate and the local H2/CO ratio. In addition to
the impact on the behaviour of H2 and CO, the composition of
intra-pellet products also affects the diffusion and solubility of indi-
vidual hydrocarbon species. In particular, the diffusion and solubility
Article
a b
80
Probability density
function (a.u.)
70
60
NC
50
40
Fig. 6 | Carbon number distributions within an individual catalyst pellet. a,
Zoomed-in map of NC from catalyst layer 3 acquired at feed ratio of 0.5 (shown in
Fig. 5a). b, Histograms of NC from within the highlighted pellet in a (purple box),
for the three feed ratios studied. c, Distributions of carbon number for each of
of olefins have been reported to affect the readsorption of these species
on the catalyst surface and hence affect catalyst selectivity26. Of course,
the spatial heterogeneity in the NC within pellets and catalyst layers
shown in Figs. 5 and 6 will also lead to further heterogeneity in the dif-
fusion and solubility of reactants and products.
Ex situ measurements of intra-pellet product distribution have
been conducted previously21,29. These have shown an NC of the
intra-pellet products of ~36 (ref. 21) and ~45 (ref. 36) at feed ratios of 2
and 1, respectively, for a cobalt catalyst, and ~37 at a feed ratio of 2
(ref. 29) for a cobalt–ruthenium catalyst. These results are consistent
with the operando data reported in this paper that were acquired at
the same feed ratios despite using a different catalyst, and they rein-
force the observation that the intra-pellet wax composition is signifi-
cantly different from that of the wax collected at the reactor outlet.
Operando characterization of water in pores
To understand how the reaction proceeds inside the catalyst pores, it
is important to track not just hydrocarbon formation but also water
production and the phase and environment in which it exists, because of
its impact on catalyst activity31,37, selectivity31 and stability37,38. Figure 8
shows a 2D spin–lattice relaxation time versus chemical shift spectrum
in which 1H-containing species that share overlapping chemical shift
signals are spectrally resolved through their nuclear spin–lattice (T1)
relaxation times, which have been shown to be an indicator of sur-
face interaction39,40. Figure 8 confirms that oxygenates and water are
formed along with hydrocarbons. The chemical shift and T1 relaxation
time of the water signal provide insight into the phase of the water.
The chemical shift of the water signal at 3–5 ppm identifies the water as
being in a water-rich liquid phase; gas-phase water and dilute water in
the wax phase would have a chemical shift of ~0 ppm (ref. 39). Moreover
the T1 value associated with the water of 10−3–10−2 s is characteristic
of water interacting with the pore surface; water existing in the pore
centre would have a T1 of ~1 s (ref. 39). The observation of a water-rich
layer covering the surface and coexisting with wax is consistent with the
predictions of molecular dynamics simulations for the case of hydro-
philic pores22. This had not, until the present work, been confirmed
under operando conditions, to the best of our knowledge. Using the
signal intensity in the 2D spectra, the weight fraction of surface water in
the intra-pellet liquid was calculated as 0.57 ± 0.05 wt%, 0.16 ± 0.07 wt%
and 0.05 ± 0.04 wt% for feed ratios of 2, 1 and 0.5, respectively (error
analysis in Methods). The decrease of water composition is consistent
with the decrease in CO conversion as feed ratio decreases. These meas-
urements are currently being combined with the MRI modality to gain
far greater insight into the role of water during the FT process, along
with the characterization of oxygenate species. These studies will be
extended to catalysts of different formulation and physical structure.
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
0.3 c 0.07
FR = 2 FR = 2
FR = 1
Mole fraction (a.u.)
FR = 1
0.2 FR = 0.5 FR = 0.5
0.1
0 0
30 40 50 60 70 0 20 40 60 80 100 120
NC NC
the three feed ratios studied from the pixel identified by the arrow in
a. The shadow regions in c indicate the standard error (s.e.) of the distributions
estimated using three repeat measurements (n = 3). The result at each carbon
number is presented as the mean value ± s.e.
Conclusions
This work reports operando imaging of the product distribution
formed within individual catalyst pellets during FT synthesis in a
pilot fixed-bed reactor; the work is performed at industrial reaction
conditions and in catalyst pellets and a reactor of an industrially
relevant scale. These data demonstrate the importance of oper-
ando studies at these length scales if the real catalytic process is to
be understood. Such insights complement operando studies at the
nanoscale, which focus more on the intrinsic catalytic activity of a
catalytic material. The significance of being able to study the cata-
lyst working at the pellet and reactor scales is that the study includes
the effect of mass transfer processes on the overall catalytic process,
which can substantially modify the catalytic performance from that
which is expected from the feed composition and reactor operating
conditions.
The data reported show two main results. First, the carbon number
distribution within the pores of the catalyst decreases with an increase
in the saturation of the pores with hydrocarbon product. Second, while
GC data suggest a start-up time to steady-state behaviour over time-
scales of ~51 h, the magnetic resonance data show that this is actually
the timescale over which saturation of the pore space is occurring,
and that liquid distribution throughout the reactor takes considerably
longer to reach a steady state. Within the particular layer of the catalyst
bed reported, the molecular diffusivity of the hydrocarbon products
is still evolving at ~500 h TOS. During this time, the product distribu-
tion is changing and hence so will the diffusivity of the H2 and CO gases
within the pore space, which are sensitive to the carbon number of the
wax in which they are diffusing. Further, the solubility of these gases
in the wax inside the pores will change over these timescales, and the
H2/CO ratio will deviate significantly from that expected from the
feed condition.
Spatially resolved maps of the molecular diffusion coefficients of
product hydrocarbon species within the pellets are reported, and from
these, maps of average hydrocarbon chain length are calculated. These
data are consistent with the predictions of the Anderson–Schulz–Flory
mechanism: heavier hydrocarbon chains are produced at lower
H2/CO feed ratios. The product distribution is also seen to broaden with
a decrease in feed ratio. Importantly, the data show that significantly
heavier hydrocarbon chains exist within the pore space of the catalyst
than are produced in the product wax collected at the exit of the reac-
tor. Such measurements made under operando conditions provide
important data and insight in the context of more accurate model-
ling of the FT catalytic process. Operando 2D NMR spectroscopy also
confirms the presence of water inside the reactor and that this water
exists in the form of a water-rich liquid phase at the surface of the pores
within the catalyst pellets.
Article https://doi.org/10.1038/s41929-023-00913-8

a b Intra-pellet liquid c Intra-pellet liquid

70 1.6 0.6 600
Intra-pellet liquid H2 H2

Henry’s constant (bar)

De of CO (10–8 m2 s–1)
De of H2 (10–8 m2 s–1)
60 Collected wax 1.5 500
CO CO
0.5
50 1.4 400
NC

40 1.3 300
0.4
30 1.2 200

20 1.1 0.3 100

0.5 1.0 1.5 2.0 20 30 40 50 60 70 80 20 30 40 50 60 70 80
H2/CO feed ratio NC NC

Fig. 7 | Comparison between the intra-pellet liquid products and collected values. The values were calculated according to the method of Marano and
wax. a, NC of the intra-pellet products in the reactor averaged over all layers are Holder35. The black dashed vertical lines in b and c indicate the values calculated
compared with those of the wax collected at the reactor exit for the three feed for NC = 28, a value commonly used in the literature. The shaded areas in b and c
ratios studied. The NC values have standard errors of ~1 as estimated using three indicate the diffusion and solubility at the true composition of the intra-pellet
repeat measurements. b, Effective diffusivity, De, of H2 and CO dissolved in wax liquid as determined in this work. The lower and upper bounds of NC in the
mixtures of different NC values. The De values were calculated according to shaded areas are the NC values measured at catalyst layer 1 for FR = 2, and at
Zheng et al.48. c, Henry’s law constant of H2 and CO in wax mixtures of different NC catalyst layer 3 for FR = 0.5, respectively.

1 cylinders were mixed before entering the top of the reactor. The gas
Intensity (a.u.)

flow rates were controlled by mass flow meters calibrated to measure

flow rates in the range 0.5–30 NL h−1, where NL is a normal litre defined
as the mass of 1 litre of gas at a pressure of 1 atmosphere and a tem-
0 Population (a.u.) perature of 20 °C. The flow rate of the effluent gas was measured with
0 1 a calibrated wet gas flow meter. Trace heating was mounted along the
2
10
Hydrocarbons feed and effluent lines of the rig and on the external wall of the reactor
1 to provide heating as required. The temperature of the catalyst bed was
10
measured by two thermocouples located above and below the catalyst
bed inside the reactor; the temperature was controlled to an accuracy
T1 relaxation time (s)

0
10
of ±0.5 °C. The pressure of the reactor was controlled to an accuracy
–1
of ±0.1 bar with an Equilibar back pressure controller installed down-
10
Oxygenates stream of the reactor. The reactor rig was controlled by the National
–2
Instruments LabVIEW application. The wax products (mainly C10+)
10
were collected from the reactor outlet and analysed offline using GC.
–3 Water The gas-phase products (mainly C1–C5) and unreacted feed gases were
10
flowed to another GC instrument for online composition analysis.
–4
10
20 15 10 5 0 –5 –10 Experimental procedure
Chemical shift (ppm) Throughout the experiment, ramp rates of 1 °C min−1 and 0.3 bar min−1
were used for temperature and pressure operation, respectively. Prior
Fig. 8 | Operando characterization of water in catalyst pores. The 2D
1
H spectrum, correlating chemical shift and T1 relaxation time, is used to
to the FT reaction, the liquid–gas separators for wax products (vessels 3
discriminate hydrocarbons, oxygenates and water present in the reactor. The and 4 in Fig. 1a) were heated to 160 °C and 140 °C, respectively, and the
1D projections of the 2D spectrum onto the chemical shift and T1 axes are also liquid–gas separator for light products (vessel 5 in Fig. 1a) was cooled to
shown. The chemical shift is relative to the 1H resonance of tetramethylsilane. 3 °C. The gas feed and effluent lines were heated to 220 °C and 170 °C,
respectively. Before starting the reaction, the catalyst was reduced
in situ at 250 °C and 6 bar in a H2–N2 flow with a H2 flow of 1 NL h−1 and N2
flow of 20 NL h−1. The reduction took 40 h and was considered complete
Methods when there was no change in the H2 concentration in the effluent gas as
Materials measured by GC. After the catalyst reduction, the H2 flow was turned off
The catalyst, provided by Shell, has a Brunauer–Emmett–Teller surface and the N2 flow rate was reduced to 3 NL h−1. The reactor was cooled to
area of 44.8 m2 g−1, a Barrett–Joyner–Halenda average pore diameter 160 °C and depressurized to ambient pressure. After reaching 160 °C,
of 28.6 nm and a pore volume of 0.34 cm3 g−1 as measured by nitrogen the reactor was pressurized to 37 bar at a N2 flow of 30 NL h−1. At 37 bar,
sorption analysis. The Ru metal surface area, crystallite size and disper- H2 was flowed into the reactor at a flow rate of 30 NL h−1 with the N2 flow
sion were measured by oxygen chemisorption41 as 0.39 m2 g−1, 10.4 nm reduced to 9 NL h−1 such that the N2 gas in the reactor was replaced with
and 7.2%, respectively. The high purity silicon carbide (SiC) used to the H2–N2 gas mixture. This process took ~40 min as confirmed by no
dilute the catalyst bed was provided by Fiven. The gases used in the change in effluent gas composition as measured by GC. After this, the
reaction experiment—CO (purity, >99.997%), H2 (purity, >99.999%) H2 and N2 flow rates were reduced to 6 NL h−1 and 1.8 NL h−1, respectively,
and N2 (purity, >99.999%)—were obtained from BOC. and the CO gas was flowed into the reactor at the appropriate flow rate
to deliver the required feed ratio. In the first experiment, the CO flow
Operation of the reactor was set to 3 NL h−1 to give a feed ratio of 2. The gases H2, CO and N2 were
The reaction rig consists of a gas feed section, a reactor and a product used as the reaction feed gases. With these flow rates of feed gases and
collection section. The CO, H2 and N2 gases from the compressed gas the reactor pressure maintained at 37 bar, the reactor temperature was

Nature Catalysis
Article
increased to 220 °C and the reaction was started from a dry reactor.
After completing the MRI and 2D NMR measurements at feed ratio 2,
the feed ratio was reduced to 1 by adjusting the feed H2 and N2 flow rates
to 3 NL h–1 and 4.8 NL h−1, respectively, while the CO flow rate was main-
tained at 3 NL h−1. After reaching the steady state at feed ratio 1, MRI
and 2D NMR measurements were carried out. The feed ratio was then
changed to 0.5 by adjusting the feed H2 and N2 flow rates to 1.5 NL h–1
and 6.3 NL h−1, respectively, with the CO flow rate maintained at 3 NL h−1.
After the measurement at feed ratio 0.5, the feed ratio was adjusted
back to 2 following the same operation procedure to check catalyst
stability. A constant weight hourly space velocity of 4 NL h−1 gcat−1
(gcat, grams of catalyst) was used during the experiment. The total TOS
of the reaction to complete all experiments was >3,000 h. No change
in the catalyst bed position throughout the experiment was confirmed
by comparing the images acquired at the beginning and the end of the
experiment (Supplementary Fig. 7).
GC measurement
GC was used to characterize the carbon number distributions of the wax
products collected from the reactor exit and the composition of the
reactor effluent gas mixture. For the characterization of wax composi-
tions, a Thermo Scientific (Trace GC-Ultra) GC instrument equipped
with a flame ionization detector was used. The effluent gas composi-
tions were measured using an Agilent Refinery Gas Analyser (Fast RGA
7890B-0378), which contains three detection channels (two thermal
conductivity detectors and one flame ionization detector). The GC
was calibrated to measure compositions to an accuracy of ±0.5 mol%.
Magnetic resonance measurements
The NMR measurements were performed on a Bruker Avance III HD
spectrometer equipped with a vertical super-wide-bore 7.1 T super-
conducting magnet and a three-axis gradient set providing a maximum
gradient strength of 83.24 G cm−1 in each direction. A birdcage r.f. coil
of 66 mm inner diameter was used and tuned to a resonance frequency
of 300.14 MHz for 1H observation. The 1H NMR/MRI data were acquired
with a typical 1H 90° pulse duration of 65 μs.
The total signal intensity of a catalyst layer (Fig. 3b) was measured
using a 1D imaging sequence (default Bruker ‘improf’ sequence). The
2D slice-selective intensity images of the three catalyst layers were
acquired using a rapid acquisition with relaxation enhancement (RARE)
sequence42 with soft pulses applied at the beginning and the end of the
sequence for slice selection, as shown in Supplementary Fig. 8a. The
Gaussian-shape slice-selective soft pulses were 512 μs in duration and
were applied to select horizontal slices with a slice thickness of 3 mm.
The positions of the selected slices for the three catalyst layers are indi-
cated in Supplementary Fig. 9. The 3D image of the reactor was acquired
using the Bruker default RARE sequence. The parameters used in these
pulse sequences are summarized in Supplementary Tables 1 and 2.
The diffusion coefficient, D, values of catalyst layer 1 during the
reaction start-up (Fig. 3c) were measured using the 13-interval alternat-
ing pulsed gradient stimulated echo (APGSTE) sequence43 followed by
1D imaging along the reactor axial direction (Supplementary Fig. 8b).
The 2D images of diffusion coefficients were acquired with a 2D RARE
sequence preconditioned with the APGSTE sequence (Supplementary
Fig. 8c). The 2D images were acquired from 3 mm slices along the axial
direction of the reactor (Supplementary Fig. 9). All the diffusion meas-
urements were performed with a r.f. pulse spacing time, τ, of 4.3 ms.
The pulsed gradient was applied along the x direction, perpendicular
to the axial direction of the reactor, with a gradient stabilization time of
1 ms. The parameters for pulsed field gradient measurements, includ-
ing pulse duration, δ, diffusion observation time, Δ, and pulsed gradient
strength, g, used at different feed ratios are summarized in Supplemen-
tary Table 3. A diffusion observation time of 20 ms was used at a feed
ratio of 2. The observation time was increased to 40 ms for feed ratios
1 and 0.5 because of the lower molecular diffusion coefficients observed
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
under these conditions. Using these combinations of observation time
and characteristic molecular diffusion coefficients at each feed ratio
yields a root mean square displacement during the diffusion meas-
urement of ~5 μm, significantly larger than the pore size of 28.6 nm,
for all feed ratios. Further increase of Δ did not influence the results.
A recycle time of 3 s was applied in the diffusion measurements, which
is comparable to the average T1 relaxation time of the reaction mixture.
The effect of T1 relaxation weighting on the resulting diffusion coef-
ficient and carbon number distributions was considered negligible as
reported by Williams44. Other parameters used in the pulse sequences
are summarized in Supplementary Tables 1 and 2.
The 2D COSY and double quantum filtered COSY (DQF-COSY)
data were acquired to determine the average carbon number of the
products using the Bruker default pulse sequences ‘cosygpqf’ and
‘cosygpmfqf’, respectively. In both measurements, the direct and indi-
rect 1H frequency dimensions were sampled using 1,024 × 256 complex
points, respectively. Other parameters are listed in Supplementary
Table 1. The COSY and DQF-COSY data were not acquired with spatial
resolution because of signal-to-noise ratio limitations.
The measurement of T1 relaxation time was achieved using a satu-
ration recovery sequence45. A list of variable delays increasing expo-
nentially from 1 ms to 40 s in 64 steps was used for T1 encoding. Other
parameters are reported in Supplementary Table 1. The T1 measurement
was performed without spatial resolution.
With respect to relaxation contrast, the spin–spin relaxation
times, T2 and T2*, of the intra-pellet products are 100–300 ms and
~3 ms, respectively. The relaxation time of liquid in the inter-pellet
space, which is in contact with SiC particles, is at least one order of
magnitude faster than the intra-pellet values for both relaxation times.
Relevant echo times of the pulse sequences used are given in Supple-
mentary Table 1. Only T2 weighting is relevant to these acquisitions.
Given the T2 distribution of intra-pellet products and the echo times of
the diffusion sequences, the bias to the diffusion and carbon number
distributions caused by the range of T2 weighting for different species
is estimated to be no greater than one carbon number. In the presence
of significant field inhomogeneity, the signal of the gas-phase species in
the inter-pellet space is negligible due to low 1H density and fast
signal relaxation46.
Data processing for the magnetic resonance measurements
The 1D, 2D and 3D intensity images were processed by 1D, 2D and 3D
Fourier transform, respectively. For the images acquired with APGSTE
preconditioning, a diffusion-weighted 1D or 2D image was obtained at
each value of gradient strength, g, by 1D or 2D Fourier transform. A
pulsed field gradient decay was obtained at each image pixel, and an
inverse Laplace transform was applied to these data to yield a diffusion
distribution from which the average diffusivity, D , was calculated. The
inverse Laplace transform was performed using the method of Tik-
honov regularization47. In the implementation of Tikhonov regulariza-
tion, a smoothing parameter must first be determined. In this work,
this parameter was determined using the method by Butler–Reeds–
Dawson, which is robust for data with a limiting signal-to-noise ratio47.
For the results of COSY and DQF-COSY, sine window functions were
applied to both time-domain dimensions, and the indirect dimension
was then zero filled to 1,024 points. The resulting 2D dataset was Fou-
rier transformed to obtain the 2D spectrum, which was then modulus
corrected and symmetrized against the diagonal of the spectrum.
Baseline correction was then applied. The analysis of the 2D spectra
was performed on the 1D anti-diagonal spectra, which were obtained
by integrating the 2D spectra along the diagonals over the whole chemi-
cal shift range32.
For the T1 relaxation measurement, the time-domain data acquired
at each delay value were Fourier transformed to produce a spectrum.
For each value of chemical shift, a T1 relaxation recovery dataset was
then extracted and processed using the inverse Laplace transform to
Article
yield a distribution of relaxation times associated with that chemical
shift value. In this way, a 2D chemical shift versus T1 relaxation spectrum
was obtained.
Error analysis
The APGSTE-preconditioned RARE imaging of each catalyst layer was
repeated three times at the steady state at feed ratio 2. The repeat
measurements were used to estimate the error of D and NC. In the 2D
images of the catalyst layers, pixels that had poor data quality due to
low signal-to-noise ratio were identified as those where the standard
deviations of NC were larger than five carbon numbers. These pixels
were removed from the D and NC maps. The error of NC calculated based
on 2D NMR spectra was estimated by considering error propagation
of the uncertainties of fit parameters in equation (3) and of experimen-
tal measurement. The standard deviations (s.d.) of water weight frac-
tions were estimated using 29, 80 and 33 repeat measurements (n = 29,
80 and 33) at the steady state for a feed ratio of 2, 1 and 0.5, respectively.
The results are reported as mean values ± s.d.
Transformation of diffusion to carbon number distributions
The technique described by Williams et al.23 was used to transform
the distributions of molecular diffusion coefficient obtained from
the APGSTE-preconditioned imaging measurements to carbon num-
ber distributions. A relationship between the carbon number Ni of a
component in a mixture of linear hydrocarbons can be expressed as a
function of its diffusion coefficient Di (ref. 24):
1 ∞
−β
A v 1 v+β
−1
Ni = ( ) (A v φ) , φ = ∫ Di v P (Di ) dDi , (2)
Di
0
where A, β and the Flory exponent, v, are parameters that depend on
temperature and the degree of confinement of the mixture but are
independent of pressure; P is a probability density function.
Following the methodology described by Williams et al.23, the
parameters A, β and v were calibrated at the reaction temperature
of 220 °C using liquid mixtures (or waxes) confined within the same
porous titania as the catalyst support material used in the FT experi-
ments. Two wax mixtures, consisting of known distributions of chain
lengths of n-alkanes, were used in the calibration. Their carbon number
distributions, determined by GC, are shown in Supplementary Fig. 10;
to the nearest integer, the average carbon number of each is 35 and 42,
respectively. The data were used to calibrate the parameters in equa-
tion (2); the resulting parameters are A = 2.22 × 10−7 m2 s−1, β = 0.27 and
v = 1.41. The carbon number distributions obtained based on these
calibrated parameters are plotted in Supplementary Fig. 10, from which
average carbon numbers of 34 and 41 are obtained, consistent with the
GC analysis. The calibration experiments also allow the determination
of a noise threshold value of 0.086 required in the Butler–Reeds–Daw-
son method, which was applied to determine the smoothing parameter
employed in Tikhonov regularization47.
Determination of average carbon numbers using 2D NMR
The ratio between the intensities of the cross and diagonal peaks IXP/Idiag
of the COSY spectra of n-alkanes or n-alkane mixtures has been
reported to decrease with increasing carbon number NC or average
carbon number NC following a power law relationship independent of
temperature32:
−b
IXP /Idiag (NC ) = a (NC ) . (3)
The parameters a and b have been determined using the COSY
spectra of n-alkanes and n-alkane mixtures for which NC and NC were in
the range 5–40 (ref. 32). However, the cross peaks of the COSY spectra
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
acquired from the reactor were severely distorted by an artefact along
the indirect dimension, commonly known as the t1 artefact. This arte-
fact was significantly reduced in the DQF-COSY spectra obtained from
the same system. Therefore, in this work, the cross peak intensity was
obtained from the DQF-COSY spectra while the diagonal peak intensity
was still acquired from the COSY spectra. Hence, the value of parameter
b from the original reference32 is used directly, whereas the value of
parameter a needs to be adjusted to account for the difference between
the signal intensities of the cross peaks of the DQF-COSY and COSY
spectra. The parameter a was determined using the DQF-COSY and
COSY spectra of pure n-alkanes with carbon numbers in the range 6–16
confined in the titania support of the FT catalyst and at ambient tem-
perature. The calibration data are shown in Supplementary Fig. 11a,
and equation (3) was fitted to these data by setting the parameter b as
the reported value32. The fit curve is also presented in Supplementary
Fig. 11a. The resulting values of a = 0.362 ± 0.007 and b = 1.44 ± 0.02
(uncertainties are standard errors of the fit) were used to determine
the average carbon numbers present in the reacting system. The IXP and
Idiag values were obtained by integrating the anti-diagonal spectra of
the 2D spectra. The anti-diagonal spectra of the DQF-COSY and COSY
spectra shown in Supplementary Fig. 11b,c are presented in Supple-
mentary Fig. 11d,e, respectively. The cross peak in Supplementary
Fig. 11d and the diagonal peak in Supplementary Fig. 11e, which were
used to calculate IXP and Idiag, are highlighted in the figures.
The signal detected in DQF-COSY and COSY measurements was
predominately associated with intra-pellet products; the signal associ-
ated with inter-pellet products was negligible due to the significant T2
relaxation effects. This was confirmed by a 2D NMR experiment that
selectively measured the data from the reactor regions packed with SiC
particles; negligible signal was detected from these regions. Therefore,
the average carbon number determined by COSY and DQF-COSY was
associated with intra-pellet products.
Data availability
The data that are used to produce the main text figures are available at
https://doi.org/10.17863/CAM.92264. All data in the study are available
from the corresponding author upon reasonable request.
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Acknowledgements
We thank P. Munnik for catalyst synthesis and J. Chen for calculations
and simulation studies supporting this work. This work was funded
by Shell Global Solutions International B.V. Q.Z. thanks the IChemE
Andrew Fellowship for additional financial support. For the purpose
of open access, the authors have applied a Creative Commons
Attribution (CC BY) licence to any Author Accepted Manuscript version
arising from this submission.
Author contributions
Q.Z. led the experimental design, the data acquisition and
interpretation and the writing of the manuscript. J.W. was also involved
in the data collection, and developed and applied the analysis for
transforming the diffusion measurements into hydrocarbon chain
length data. L.R.v.T. and S.V.E. contributed to the experimental design
and data acquisition, and design of the reaction engineering set-up.
T.A.B. and C.M.G. helped design the experiments and provided the
catalyst materials. L.F.G., M.D.M. and A.J.S. oversaw the project and
worked with the coauthors to analyse and interpret the data obtained.
Nature Catalysis
https://doi.org/10.1038/s41929-023-00913-8
J.W., T.A.B., G.L.B., C.M.G., M.D.M., A.J.S. and L.F.G. edited and revised
the manuscript.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information The online version contains
supplementary material available at
https://doi.org/10.1038/s41929-023-00913-8.
Correspondence and requests for materials should be addressed to
Lynn F. Gladden.
Peer review information Nature Catalysis thanks the anonymous
reviewers for their contribution to the peer review of this work.
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