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Ubc 2007-266861
Ubc 2007-266861
mf
As U
m
f for the FCC (0.0026 m/s) is significantly lower than the range of measured particle
velocities (0.01 to 0.04 m/s), the effect of this gas slip is ignored. If a voidage of 50%in the
annular solids is assumed, the volumetric flow of gas dragged down in the annulus should be just
slightly less than the measured solids circulation, expressed in the same units. The helium tracer
data in fact supports this. In all but one run, the flow of annular gas circulation estimated from the
helium tracer data is within 30%of the solids circulation obtained by measuring the downward
velocity of the annular solids at the wall.
One key benefit claimed for the ICFBMR concept is that addition of air does not significantly
reduce the membrane flux, as the bulk of the nitrogen in the air quickly leaves into the freeboard
82
and beyond without affecting the hydrogen partial pressure in the reactor core where the
membranes are located. This feature is verified in the helium tracer data. In all but one run, the
amount of helium circulated to the core from the annulus was only approximately 10%of the
total helium added to the column. As the data from run #2 illustrate, however, it is clear that the
top of the column needs to be well mixed with uniform flow through the core to benefit fully
from this reactor feature.
The helium concentration measured at the top of the core channels tended to be higher than at the
middle. From this finding, it seems likely that some solids from above the core box were drawn
down into the upper regions of the core flow channels.
Measured helium concentrations in the core with solid panels tended to vary more than for the
slotted panels, especially for channels 1 and 8 at either edge of the core box. This is as expected,
as gases within the core channels can interchange with the slotted panels, but not with the solid
(impervious) panels. In addition, channels may plug when operating with the solid panels,
leading to uneven gas distribution, whereas the flow is much more uniform when adjacent panels
can "communicate"with each other.
83
Table3.4: Summary of cold model helium tracer results
(all %listed in table are vol%)
Core panel geometry Solid Danels Horizontally slotted panels Vertically slotted panels
Run number 1 2 3 4 7 6 8 9
Main airf l ow (SLM) 94 240 480 713 240 480 240 480
Seconday air flow (SLM) 20 20 20 20 20 20 20 20
Oxidant air flow (SLM) 70 70 140 210 90 155 70 140
Helium flow (SLM) 22. 7 22. 7 28.3 21.4 22.7 28. 3 22. 7 24. 2
Gas velocity in core (m/s) 0.09 0.23 0.46 0.68 0.23 0.46 0.23 0.46
[Helium] in oxidant supply 24 . 5% 24 . 5% 16. 8% 9. 3% 20. 1 % 15. 4% 24 . 5% 14. 7%
[Helium] in column exit 11. 0% 6. 4% 4. 2% 2. 2% 6. 1 % 4 . 1 % 6. 4% 3. 6%
Helium measurements [He] % St. dev. [He] % St. dev. (He] % St. dev. [He] % St. dev. [He] % St. dev. [He] % St. dev. [He]% St. dev. [He] % St. dev.
S
a
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)
East quadrant - bottom (325) 27.91 2.20 20. 64 1.12 3.02 1.54 5.83 0.32 4.68 0.43 3.11 0.43 3.71 0.31 3.15 0.39
S
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West quadrant - bottom (325) 33. 38 0.16 17.63 2.21 4.11 0.88 2.76 1.03 3.27 0.39 4.83 0.26 6.26 0.33 4.80 0.18
S
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North quadrant - bottom (325) 29. 62 0.74 23. 40 0.29 5.70 0.71 5.06 0.41 4.00 0.21
S
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)
South quadrant - bottom (325) 33. 59 0.08 19.08 2.29 4.61 4.11 5.11 0.40 3.03 1.44 0.96 0.31 4.68 0.36
S
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)
Channel 4 - bottom (230) 15. 10 1.45 7.68 2.55 0.56 0.15
S
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)
Channel 5 - bottom (230) 11.66 0.80 8.64 1.71
S
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)
Channel 1 - mid height (862) 8.57 1.74 0.46 0.26 0.98 0.13 0.42 0.28 0.36 0.43 0.19 0.13 0.46 0.06
S
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Channel 2 - mid height (862) 2.33 1.38 -0.58 0.16 0.02 0.23 1.46 0.11 0.18 0.07 0.10 0.09 0.13 0.14
S
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)
Channel 3 - mid height (862) 5.48 0.33 0.62 0.19 0.21 0.04 0.41 0.05 0.60 0.14 0.60 0.09 0.71 0.08
S
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)
Channel 4 - mid height (862) 2.90 0.40 0.39 0.22 0.16 0.04 0.56 0.15 0.37 0.09 0.35 0.09 0.36 0.12
S
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)
Channel 5 - mid height (862) 5.10 0.76 0.54 0.19 0.58 0.12 0.32 0.13 -0.22 0.02 0.59 0.11 ' 0.73 0.13
S
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Channel 6 - mid height (862) 4.11 0.89 0.51 0.23 0.21 0.10 0.39 0.14 0.30 0.06 0.57 0.11 0.54 0.16
S
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Channel 7 - mid height (862) 1.36 0.19 0.11 0.16 0.00 0.13 0.54 0.12 0.26 0.05 0.67 0.15 0.31 0.08
S
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Channel 8 - mid height (862) 4.21 0.09 1.86 0.20 0.37 0.20 0.58 0.16 0.24 0.10 2.56 0.59 1.47 0.22
S
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Channel 4 - top (1494) 3.43 0.12 4.87 0.72 1.45 0.43 0.49 0.16
S
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Channel 5-top (1494) 3.38 0.16 3.42 2.24 0.92 0.27 0.83 0.36
S
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Channel 6 - top (1494) 4.34 0.98 1.26 0.29 0.38 0.08
Average of all quadrants - bottom 31.1 20. 2 2.47 3.9 0.81 4.8 1.43 3.7 0.89 4.3 1.90 5.0 1.80 4.2 0.76
Average of all channels at mid-height 4.3 2.23 0.49 0.68 0.32 0.33 0.58 0.36 0.26 0.23 0.70 0.78 0.46 0.41
Estimate of annular gas downflow (SLM) 64 69 50 46 31 39 60
Measured solids circulation (LPM) 14 39 64 71 36 55 51 82
Fraction of helium recycled 57% 10% 1 1 % 7% 5% 9 % 1 0%
3.5.4.2 Helium Addition to Core - Vertically Slotted Panels
An investigation into gas mixing with the reactor core equipped with the vertically slotted panels was
also attempted. For this set of experiments, helium was added to the bottom of channel number 4 for
a period of 10 minutes, and the helium concentration was monitored at locations higher up the core
box. The cold model operating conditions for the tests were:
Main air flow 240 SLM;
Secondary air 20SLM;
No oxidant air flow;
6.0SLM helium flow added to flow channel 4, 130 mm above the bottom of the core box.
The 10-minute helium addition test was repeated four times for four different core sampling points: at
top of channels 4, 5 and 6 and at mid-height of channel 8. See Figure A3.2.7 in Appendix 3.2 for the
plan view of the core box and the locations of the sample points. Results are presented in Figure 3.19.
Figure 3.19: Measured helium concentration (vol%) at different sample points in upper core box after
10 minute continuous injection of helium into bottom of channel 4 (vertically slotted panels)
As all sampling exhibited a system response delay of several minutes due to the long sampling lines
and low sampling flow rates, no conclusions on the dynamic response of the system could be drawn.
The average helium concentrations at the top of channels 4 and 5 were 2.2%and 2.1%respectively,
close to the concentration in the column exit. The average helium concentrations at the top of channel
6 and the middle of channel 8 were significantly lower, 0.8%and 0.7%respectively.
As noted above, the positions of the vertically slotted panels were alternated so as to create a back-
and-forth serpentine-line connection between the channels. The sample point for channels 4 and 5
were thus effectively on opposite sides of the same channel, so the similar helium concentrations are
Time after He injection (mins) Time after He injection (mins)
85
not unexpected. The sample points for channels 6 and 8 were several "U-turns"away from the
channel 4-injection point, clearly reducing gas dispersion. If the helium in channels 6 and 8 were due
solely to the circulation of gas from the annular regions, a concentration of roughly 0.4%would be
expected, so some dispersion of helium from channel 4 likely occurred through the intervening slots.
3. 6 Discussion
The cold model testing clearly showed that solid (i.e. impervious, non-communicating) membrane
panels within the core box led to poor gas-solid distribution among the core channels. Slotted,
communicating membrane panels greatly improve the uniformity within the core, and are thus
preferred in the ICFBMR design.
The pressure impulse lines in the north and south annular quadrants added flow resistance, and thus
these quadrants exhibited significantly lower solids circulation than the other two quadrants. Such
tubing and obstacles should be minimized, especially if external heating of the reactor is used, as this
will lead to non-uniform heat transfer to the annulus solids.
3.6.1 Solids Circulation
Increasing the main feed gas flow to the core draft box increased solids circulation up to a core gas
superficial velocity of approximately 0.5 m/s, at which point circulation tended to level off.
Increasing annular air from 10 SLM to 20 SLM led to a significant increase in the solids circulation
rate. A further increase in the annular air to 30 SLM resulted in only a marginal increase in solids
circulation, or in some cases, no significant change. The cold model testing clearly shows the
importance of independent control of the annular and main gas flows, especially if the reactor is to
operate at variable feed rates.
An annular flow of 10 SLM corresponds to a superficial velocity in the annulus (U
ann
) of 0.0051 m/s,
1.9 times U
m
f of the FCC particles. However, it is very likely that some of the air introduced to the
annulus did not flow up the annulus, but rather was dragged into the core draft box, as noted in earlier
ICFB studies (e.g. Song et al., 1997, Namkung, 2000). An estimate of the amount of annular gas
bypassing to the core is difficult to infer from the cold model data. Annular gas bypassing to the core
would be an important design parameter if the annular gas was to be chemically used in the annulus,
such as air for oxidation. In the ICFBMR design, however, the annulus gas can be compositionally
identical to the main feed (i.e. steam and methane) and transfer of the annulus gas to the core
improves utilization of the reactor feed. Bypassing of feed gas up the annulus would result in lower
utilization of natural gas for reforming and H
2
permeation, but this quantity is judged to be small
86
(<5%of total natural gas feed) and the annular gas would still be available for oxidation in the upper
reactor.
Of the four retained hydrodynamic scaling parameters discussed earlier in this chapter, only the last
term, Gpcore / pp Ucore, contains the solids flux (Gpcore). This scaling parameter suggests that a plot of
circulation flux vs. pp Ucore in the cold model should provide a reasonable estimate of that in the hot
reforming reactor. Figure 3.15 presented above showed the solids circulation rate (mpcore, kg/s) as a
function of the core superficial velocity (Ucore). Given an open area available to flow in the core (Acore
= 0.0188 m
2
), the FCC particle density (1,600 kg/m
3
) and assuming an annular voidage of 0.5, these
data are transformed into solids fluxes (see Figure 3.20 below).
0 200 400 600 800 1,000 1,200
Pro duct o f co re superf icial velo city and particle density (kg/m2 s)
Figure 3.20: Measured cold model solids flux in core draft box (Gpcore) for horizontally slotted and
vertically slotted panels vs. product of superficial gas velocity in core (Ucore) and particle
density (pp), with an annular air flow of 20 SLM
If the geometry of the cold model is maintained, the regression curves in Figure 3.20 are useful
design tools to estimate the solids circulation rate in the hot ICFBMR. Note that the calculated solids
flux is based on the cross-sectional area open to flow in the core (i.e. inner area of core draft box less
area blocked by panels). The catalyst particle density (pp) in the ICFBMR pilot reactor was
approximately 30%higher than that of the FCC particles in the cold model. This implies that in order
to achieve a certain solids flux, the required core velocity in the hot ICFBMR would be less than for
the cold model.
87
The question of what factors control the solids circulation rate remains. Several studies have been
conducted on fluidized beds or spouted beds fitted with draft tubes to generate an internal circulation
of particles similar to the ICFBMR concept. Most of these studies have used a configuration where
the annulus turn into the core draft tube restricts the flow, whether through orifices or by the gap
under the draft tube (i.e. Milne et al., 1992, Song et al., 1997, Shih et al., 2003). In this case, the
annular turn area (orifice or gap) is smaller than the annular area, and the pressure drop over the gap
between the annulus and the draft tube (AP
0
) determines the solids flow rate, G
p
(Song et al., 1997,
adapted from Judd and Dixon, 1978):
C
0
is the particle discharge coefficient, p
an
is the density of the annulus upstream of the gap or orifice
and D
H
is the hydraulic diameter. Equation 3.11 also indicates why, after a certain point, some
researches have found that the rate of solids circulation with additional annular gas levels off, as
bubbles in the annulus reduce the annular density (p
an
n), decreasing the density difference (AP
0
)
between the core and annulus (Song et al, 1997). However in our cold model, the annular gap area
(Agap) is almost twice the annular area (A
ann
) (r = 5.3); hence the pressure drop over the annular gap is
very low and thus equation 3.11 cannot describe the solids circulation. Figure A3.2.16 in Appendix
3.2 presents the measured annular pressure vs. the measured pressure in the bottom of Channel 4
corrected to the same elevation, and shows, as expected, that the annular pressure closely follows the
core pressure.
As shown in Figures 3.11 to 3.13 presented earlier, solids circulation increases significantly when the
annular gas flow increased from 10 to 20 SLM, but did not change significantly when it was
increased beyond 20 SLM. Clearly the flow of particles down the annulus and the annular turn into
the core, restricted solids flow at 10 SLM. Perhaps an increase in bubbles near the bottom of the
annular increased the mobility of solids as they turn into the vessel core. The extra annular air may
have also helped to prevent local defluidization in the annulus.
Figures 3.11 to 3.13 also clearly show a consistent trend of core velocity on solids circulation with all
three core panels tested. For a given annular air gas flow, solids circulation increased nearly linearly
with core gas superficial velocity up to approximately 0.3 m/s, after which solids circulation tended
to level out. In a conventional bubbling fluidized bed, solids are transported vertically within the bed
in the wake of the rising bubbles, as demonstrated in Figure 3.21.
(3.11)
88
Co lo rless
so lid -
Co lo red
so lid ~
7 7
Figure 3.21: Sketches showing solids entrainment in the wake of a rising bubble
(from Kunii and Levenspiel, 1991, after photographs from Rowe and Partridge, 1965).
If solids circulation up the vessel core is primarily due to this mechanism, the solids flux in the vessel
core (Gp
XO
re) could then be described as a function of the wake fraction of the bubbles (fw) and the
volumetric bubble flow up the vessel core (Q
0
).
p,core
= (U
core
- U
mf
)p
p
(!-*) U
corePp
(1 - e)
(3.12)
At core superficial velocities below 0.3 m/s, the fluidization flow regime is likely the bubbling
regime, with the wake fraction relatively constant. For most of the testing in the cold model, U
core
U
m
f, so the circulation rate is therefore approximately proportional to U
com
.
It is further postulated that as the core superficial gas velocity is increased above 0.3 m/s, a gradual
transition to turbulent fluidization occurs, and spherical-cap bubbles are increasingly replaced by
streaking voids (see Figure 3.1), whose carrying capacity levels off to a constant value.
As previously shown in Figure 3.13, the measured solids circulation for the vertically slotted panels
was higher than for the solid panels and the horizontally slotted panels. It is not known what factors
reduced the solids circulation in the horizontally slotted panels, but perhaps it is due to disruption of
the particle-containing wakes in the rising bubbles at the communicating gaps between the channels.
The solid panels demonstrated lower circulation rates than the vertically slotted panels. This is likely
due to periodic blockages of the core flow channels. Why the solid panels show a very slightly higher
circulation rate than the horizontally slotted panels is not known.
3.6.2 Other Geometry Aspects
Some geometric aspects that could be adjusted in the ICFBMR design, but were not tested, are as
follows:
Height of core box: In the ICFBMR design, the height of the core draft box is primarily set by two
parameters: the amount of membrane surface required for permeation and the design superficial gas
89
velocity in the core (U
core
). The height of the core draft box in the cold model, 1.52 m, is the same as
in the ICFBMR pilot reactor. Song et al. (1997) found that doubling the height of the draft tube in the
ICFB system from 0.3 to 0.6 m had a negligible effect on solids circulation. If the circulation rate up
the core depends on bubble wakes as suggested above, it follows that solids circulation would be
relatively insensitive to the height of the core box.
Ratio of annular and core draft box area: If a square core draft box is used in the ICFBMR, the
dimensions of the annulus are set, with the only adjustable parameter being the distance from the
corners of the core box to the column wall. Thus, if square core box is used in the ICFBMR design,
the ratio of the annular area to the core box area will be approximately equal to that of the cold
model. However, other core box geometries, such as a rectangular or circular draft tubes, may be
preferred, as this would allow the annular area to be reduced, thus shrinking the overall volume of the
reactor (see Figure 3.22). The cold model testing indicated that for a given annular gas flow, the
solids circulation rate is a function of the core velocity. However, it is not known how much the
annulus area can be shrunk before it starts to reduce solids circulation. Arrangement of planar
membranes in a non-rectangular draft tube is an additional challenge of the alternate designs, and
testing would be required to establish the solids circulation characteristics of the different geometries.
A. Square core B. Circul ar core C. Chord layout
(col d model )
Membranes \
(annulus)
Figure 3.22: Some alternative ICFBMR layouts
Gap between distributor and draft tube: The gap below the core draft box was 100 mm in the cold
model. As the gap area under the core box is larger that the annular area, there is unlikely to be any
significant improvement on solids circulation by increasing this distance. A very large gap could lead
to increased bypassing of core gas to the annulus and possible start-up issues. The "turn" of solids
from the annulus to the core may well restrict solids circulation, but it is believed that this resistance
could be better addressed with an alternate annular air distributor design.
90
Annular distributor design: The cold model had a relatively complex secondary air distributor. The
cold model design was chosen as it approximated the design of the ICFBMR pilot reactor, where four
small sintered plugs distributed the annulus gas. In many ICFB studies, a conical distributor has been
used (i.e. Milne et al., 1992, Chu et al., 2002, Marschall et al., 1999). Song et al. (1997) tested three
distributors similar to those displayed in Figure 3.23, and reported that the solids circulation for the
flat plate and conical distributor were similar, and higher than for the conical sparger. Intuitively, the
conical distributor appears to be a better design, and indeed Song et al. concluded that the conical
distributor equipped with tuyeres was the preferred arrangement. However, this was because less
bypassing of annular gas to the core was measured with this distributor (Song et al, 1997). In the case
of the ICFBMR, bypassing of annular gas to the core is not critical. If the conical distributor could be
modified with angled jets to accelerate the solids from the annulus to the core, an increase in
circulation might be possible (Xie, 2002), but may not merit the extra fabrication complication. More
study is needed
A. Flat plate B. Conical plate C. Ring sparger
Draft tube
t t t t t t /I I \
Annular
ring
t t
t
o
Annular
windbox
Main windbox
Figure 3.23: Alternate annular distributors, adapted from Song et al. (1997)
3.6.3 Design Implications
Higher design gas velocities in the core reactor reduce the overall reactor volume. The cold modelling
suggests that a design core velocity below approximately 0.3 m/s is appropriate, as this is the highest
gas velocity at which the solids circulation flux varies nearly linearly with velocity. Above 0.3 m/s,
the solids flux levels off, which would correspond to higher temperature gradients in the reactor core.
Of course the core reactor volume also need to be sufficient for the reaction kinetics.
Figure 3.24, generated from HYSYS simulations (see Chapter 6 for description), indicates the
expected temperature gradient from the bottom to the top of the ICFBMR core as a function of solids
circulation rate for one design condition producing 50 Nm
3
/h of permeate hydrogen. If the core
91
velocity in this case is specified to be 0.25 m/s, the flow area in the hot reactor will be nearly identical
to that in the core model (0.026 m
2
). As solids circulation increases, the temperature gradient in the
reactor core is reduced. The predicted normalized membrane area is also plotted on the figure. At
lower solids circulation rates, more membrane area would be required due to three phenomena:
At lower temperatures, the permeance of the palladium foil is reduced.
At lower temperatures, the SMR equilibrium is shifted towards reactants, reducing the hydrogen
partial pressure.
Though not accounted in the data presented in Figure 3.24, reaction kinetics are slower at lower
temperatures.
50 I 1 1.0
0 I , . . I 0.7
0 2 4 6 8
Catalyst sol ids circulation (kg/s)
Figure 3.24: Effect of solids circulation on core reactor temperature drop and normalized membrane
area (conditions: 50 NmVh H
2
, steam-to-carbon molar ratio = 3, methane feed to reactor = 25
NmVh, reactor pressure 1500 kPa, feeds preheated to 650C)
From the core velocity (U
core
= 0.25 m/s) and the reformer particle density (p
p
= 2,100 kg/m
3
), the
predicted solids circulation rate is calculated to be 1.4 kg/s for vertically slotted panels based on the
regression equation in Figure 3.20 presented above. As shown in Figure 3.24, the predicted
temperature gradient in the reactor core is approximately 10C, a very reasonable value given the
large heat input required to support the reforming process. Increasing the circulation rate beyond 1.4
kg/s results in only a marginal reduction in membrane area, indicating that appropriate solids
circulation rates can be achieved in the ICFBMR for the SMR process.
92
Chapter 4. ICFBMR Pilot Plant
This chapter provides the basis on which the ICFBMR pilot reactor was designed,
constructed and tested. Process flowsheets for the pilot plant are provided, both for
external reactor heating (conventional SMR) and with direct air addition (autothermal
reforming). A semi-industrial size reactor (135 mm ID) was constructed and integrated
into an existing pilot plant, which was upgraded with an improved control system. The
nominal design basis of the updated pilot plant was 100 SLM (6Nm
3
/h) of permeate H2,
although the six planar membranes installed into the newpilot reactor were insufficient to
produce this much hydrogen. The ICFBMR pilot reactor proved to be very stable to
operate. However the large scale of the equipment made reactor modifications, such as
internals and catalyst change-outs, challenging. In addition, lowcatalyst activity affected
the reactor performance for several experiments, resulting in the pilot plant test data being
somewhat incomplete and belowinitial expectations. The pilot testing did confirm the key
features of ICFBMR concept and showed the potential for the planar membranes to
withstand the fluidized bed reforming environment. H2 permeate purity was initially very
high (>99.999%, excluding N2) for up to -180 hours of testing, after which the purity
dropped to 99.8%. The hydrogen recovery relative to the feed natural gas was relatively
low(maximum of 1.17 Nm
3
H^/Nm
3
of natural gas), as was the maximum H2 production
(17.6 SLM or 1.06 Nm
3
/h), limited by the installed membrane area.
4.1 Introduction
As described in the previous chapter, cold modelling proved that the ICFBMR concept was viable
from a hydrodynamic perspective. The ICFBMR concept was tested in a large-scale pilot reactor. Six
of the new membranes described in Chapter 2 were integrated into the reformer system to investigate
their performance under actual operating conditions.
Much of the original pilot plant utilized in the work of Adris (1994) and Roy (1998) was re-used in
this work. An externally heated bubbling bed reactor (97 mm ID, 0.66 m tall) had been employed in
93
their tests, with small-diameter tubular membranes for hydrogen withdrawl. This reactor was too
small to house the new internals (core draft box, planar membranes) of the I CF B M R design, so a
larger reactor was designed and built.
4.2 I CF MBR Reactor
Comb i ni ng the process design requirements with mechanical engineering considerations and space
constraints made the design and installation of the new I CF B M R reactor a significant undertaking.
One of the main design challenges was the operating temperature of the reactor shell, as radiant
reactor heaters were to be strapped to the exterior of the reactor, potentially raising the wal l
temperature to values not applicable for stainless steels under the A S M E pressure vessel code. A s a
result, it was decided to house the I CF B M R reactor (V-02 in Figure 4.7, presented later in this
chapter) within a large carbon steel shell (V-01), whic h acted as the pressure vessel. A n automatic
system was designed to pad the carbon steel shell with nitrogen to a pressure approximately 100 kPa
higher than the operating pressure of the inner I CF B M R reactor. The inner I CF B M R reactor only saw
a small differential pressure, and thus could be mechanically designed to pressures much lower than
the external shell design pressure (3,450 kPag). Padding the external shell also ensured that any leaks
in the inner I CF B M R reactor would result in ingress of inert nitrogen, rather than egress of
flammable gases, such as methane and hydrogen, into the confined laboratory work space.
4.2.1 Process Design
Design of the new reactor was an iterative procedure, influenced by the capacity of the existing pilot
plant equipment, the characteristics of the new planar membranes and information gained during cold
modelling experimentation. The I CF B M R reactor was designed and supplied by Noram Engineering
and fabricated by Axton Manufacturing. The final design criteria for the new pilot plant were:
Feed rate: A s the maxi mum natural gas methane feed rate of the existing natural gas compressor
and mass flow controller was 50 S L M (3 NmVh), this became the design gas feed rate. Wi th this
gas feed flow and assuming a steam-to-carbon molar ratio of 3, a design steam rate of 150 S L M
(7.2 kg/h) was established.
Hydrogen production: A n economic reformer design should have product hydrogen recoveries
approaching 214 moles of permeate H
2
per mole of CFL, fed to the reactor. It was decided to
design the pilot system for a permeate hydrogen-to-methane feed ratio of 2, equivalent to 100
S L M (6 NmVh) of H
2
.
94
Heat input: The reactor was equipped with a new preheater, external reactor heaters to supply the
process heat required for conventional SMR operation, and an oxidant delivery system which
could supply air directly to the reactor for autothermal operation.
Mechanical: Although existing components of the pilot plant constrained the operating pressure
to 1,500 kPa, the reactor design was to be sufficient to permit the reformer to operate at
approximately 3,000kPa at 650C.
The above established the design envelope for the new system. Two process flow diagrams (PFDs)
were prepared, one showing operation with external heat input, and the other with direct air addition
(Figures 4.1 and 4.2 respectively). The autothermal PFD has an air addition rate equivalent to 0.4
moles of 0
2
per mole of C H 4 feed, slightly higher than that calculated to operate the reformer
adiabatically in the absence of heat losses. The PFDs indicate that steam was to be the membrane
sweep gas, but in practice nitrogen was used. The mass and energy balances presented in the PFD
stream tables were based on HYSYS simulations.
From the PFDs, the required heat input for the internal preheater and reactor heaters was established
at 3.0 and 6.7 kW respectively (external heating, conventional SMR mode). In order to account for
heat losses and facilitate start-up, these heaters were made significantly larger than the calculated
load.
The required membrane area to produce 100 SLM of hydrogen was calculated based on the
conditions outlined in the externally heated PFD (Figure 4.1) and the membrane flux equation 4.1:
= 0.35 m
2
(4.1)
for z 50E-6 m, Q = 0.0744 mol/s, k
H
= 3.43E-7 mol/m s Pa
05
, and
E
p
= 9,180 J/mol, T= 923K, P
Hh
= 297.7E3 Pa, P
Hl
= 50E3 Pa
In the above calculation, the H
2
partial pressure was assumed to be equal to the reactor exit H
2
partial
pressure (298 kPa). The permeate H
2
partial pressure was set at 50 kPa, assuming a 50%dilution of
the permeate stream with sweep gas. These H
2
partial pressure assumptions are slightly conservative,
as the H
2
partial pressure should be slightly higher in the lower sections of the reactor, and the
permeate H
2
partial pressure lower at the sweep end of the membrane panel. A permeation
temperature of 650C was assumed. Given a nominal permeation area of 0.0258 m
2
for each
membrane, -14 double-sided membrane panels would be needed to provide sufficient area. There
A e f f =- ^ - e x p ( ^ - P H D
ku RT
,0.5 >
95
were locations for 12 double-sided and 8 single-sided panels in the ICFBMR pilot reactor, but only 6
double-sided membranes were installed due to budget and time constraints.
4.2.2 Reac tor L ay out
The ICFBMR reactor is tall and narrow, resulting from two main criteria:
Diameter - set by fluidization velocity: As described in the previous chapter, cold model testing
indicated that the solids circulation was a near-linear function of the superficial gas velocity in
the core up to a value of approximately 0.3 m/s, at which point solids circulation levelled off. The
design core velocity for the ICFBMR pilot reactor was set at 0.3 m/s at the maximum design feed
rate (50 SLMC H 4 , 150 SLM H
2
0) and an operating pressure of 1,300 kPa. The design free core
area in the reactor was thus established at 0.0025 m
2
. The dimensions of the core box was set at
~85 mm square, and the reactor diameter was then fixed at 135 mm to fit the core box
comfortably within the reactor shell, leaving sufficient annular space at the corners of the core
box to permit solids to pass through the gaps.
Height - set by membrane area: The surface area of each ICFBMR membrane panel was 0.0258
m
2
, based on the panel geometry. Twelve panels of this area would give an installed reactor
membrane area of 0.31 m
2
, close to the value of 0.35 m
2
calculated above in equation 4.1.
However, as described in Chapter 2, the effective membrane area of each panel was in
significantly less than the geometrical permeation area.
Figure 4.3 presents the dimensioned layout of the ICFBMR reactor. The main components included:
A - Reactor shell: The reactor vessel was fabricated from stainless steel. Grade 310 was used for
the main 135 mm diameter section, as this component was exposed to the external heaters. All
other vessel components were grade 304 stainless steel.
B - Core draft box: A rectangular, open-ended duct housed the membranes.
C - Membrane panels: As indicated earlier, only six panels were installed in the reactor; the
balance of the membrane places were filled with stainless steel dummy plates. Each installed
membrane panel had separate reactor connections for sweep gas and hydrogen permeate. Sweep
gas entered the top of the membrane panel, counter-current to the up-flowing reactor gases,
whereas permeated hydrogen left the bottom of the panel.
D - Main feed distributor: Preheated reactor feed was introduced into the reactor through a simple
orifice plate distributor in which 49 - 1 mm diameter holes were drilled in a pattern to match the
area of the core draft box (see Figure A4.1.1 in Appendix 4.1).
9 6
FBMR SKID ICFBMR SKID
ELECTRIC
HEATER f l
Stream t 2 i
4 5 6 7 8 9 10 11 12 14 15 16 17 18 2 0 21 22 23 24 30 31 32 33
MOM Ho- 2.04 2.04
7.0a
7.65 5.12 9.I2 9.21 8.21 0.91 6.31 6.06
6.00
8.57 8.57 4.55 3.55 6. 66 4.55 4.86 5\4i
- 0.50
4.61 266 26S 361 361
MoxFlow kq/h
Volumetric Flow mi/h i.3d 6.22 0.007 6.U 0.56 1.39 1.25 2.76 0.14 0.31 6.60 6.6o 2.63 1.47
0.46 0.664
6. 66 6.665 5.96 27.62 4.94 6.665 0.20 6. 26 6.36 6. 36
Molar Flow kmol/h 0.13 0.13 0.39 0.39 0.52 0.52 0.47 0.47 0.05 0.05 0.00 0.00 0.45 0.45 0.23 0.22 D.00 0.27 0.27 0.54 0.28 0.26 11.4 11.4 20.1 20.1
cH4 mol fract 1 0.244 6,244 6.244 6.244
0.244 0.244
0.06b
0.665 0.126
CO 6.043
0.043
O.OBJ
C02 6.176 6. 175 6.341
H20 1 1 0.756 6.756 6. 736 0.756 6.756 6.756 0.486 0.4B6 0.006 1 1 1 0.500 6.056 1 1 1 1
N2 0.790
0.730
1
02 6,210
0.210
H2 0.229 0.229 0.443 0.500. 0.950
Vapour Fraction 1 0 0.124 6.376 1 1 1 1 1 i i 1 1 1 6 1
0
i - 1 1 0 6 6 6 6
Temperature *C 10 15 15 193 147 180 180 650 180 650 15 650 650 250 40 40 15 15 133 650 40 40 15 30 15 30
Pressure kPa (abs) 150 1350 1350 1350 1350 1350 1350 1300 1350 1300 1350 1300 1300 1300 1300 1300 2000 150 150 150 150 150 150 150 150 150
MW kq/kmol 16.0 16.0 1B.0 18.0 17.3 17.5 17.5 17.5 17.5 17.5 28.9 28.9 19.2 19.2 20.4 18.0 28.0 18,0 18.0 10.0 2.8 18.0 18,0 18.0 18.0 18.0
Density kq/m3 1.03 9.3 999 51.4 18.4 6.57 6.57 2.98 6.57 3.0 16.39 4.87 3.26 5.83 10.29 992 23.7 999 0.82 0.20 0.16 992 999 995 999 995
Viscosity CP 0.011 0.011 1.14
- -
0.013 0.0)3 0.028 0.013 0.028 0.019 0.045 0.030 0.018 0.015 0.65 0.017 1.1 0.013 0.024 0.0087 6.65 1.1 o.ao 1.1 0.80
THermol Cona. W/m K 0.032 0.033 0.60
- -
0.039 0.039 0.097 0.039 0.097 0.026 0.063 0.116 0.D67 6. 661 0.63 0.025 6. 60 0.027 0.18 0.1? 0.63 0.60 0.62 0.60 0.62
Heat Copacity kJ/kqX 2. 22 2.31 4.05 4.29 3.62 2.20 2.20 2. 72 2.20 2.72 1.04 1.13 2.18 1.93 1.66 4.04 1.04 4.05 1.95 3.51 10.2 4.04 4.05 4.04 4.05 4.04
Enthalpy kW -2.66 -2.66 -3i.ia -29.22 -31.8S -28.23 -25.41 -22.73 -2.B2 - 2 . 5 3 0.00 0.00 -21.41 -23.36 -9.66 -16.97 0.00 -21.41 -17.81 -14.98 -0.93 -20.15 -905.6 -902.2 -1591.2 -1585.1
NOTE I: OXYGEN / AIRDISTRIBUTORREQUIRED
NOTE 2:MULTIPOINTTHERMOCOUPLES REQUIRED
NOTE 3: PRESSURE TAPS REQUIRED
NOTE 4: MAIN. CORE riUlDIZATION CAS
NOTE 5: ANNULUS GAS
NOTE 6: HEATER DUTIES DONOTINCLUDEHEATLOSSES
INTERNALCIRCULATING
FLUIDIZEDBEDMEMBRANE REFORMER
PROCESS FLOWDI AGRAM
50 SLM CH4 FEED, 100SLM H2. NO OXIDANT ADDITION
50% SWEEP STEAM DILUTION
B-Z0B45-13B5
Figure4.1: Process flow diagram (external heating)
FBMR SKID ICFBMR SKID
NOTE * /?> /tf> NOTE 5
Stream 1 i 1 2 i 4 5 6 7 8 9 10 11 12 14 IS 16 17 18 20 21 22 2i 24 30 31 32 33
2.04 2.04 7.6fl 7.06 9.12 9.12 B.21 B.21 6.91 6.91 S.fiS S.65 17.23 17.23 12.69 5.14 5.66 4.86 4.Bb b.41 o.ao 4,61 286 361 361
7 S
Volumetric Flo*
l.9fl 0.218 6.007 6.41 673 1.3S 1.25 176 0.14 6.31 6.S3 1.76 4.34 2.43 0.89 6.665 0.00 0.005 5.96 27.62 4.94 0.005 0.29 0.29 0.36 0.36
Motor How kmol/h 0.13 0.13 0.39 0.39 O.S2 0.52 0.47 0.47 0.05 0.05 0.30 0.30 0.73 0.73 0.45 0.29 O.OO 0.27 0,27 0.54 0.28 0.26 15.9 15.9 20.1 20.1
CM*
1
mol Iroct 1 1 0.244 6.244 6.244 6.244 6.244 6.244 6.06S 6.665 6.065
6 0.022 6.622 6,635
Cb2 6.147 6.147 0.246
H20 1 1 0.756 6.756 6.756 6.756 0.756 6.756 6.3S3 6.393 6.667 1 1 1 0.500 0.050 1 1 1 1
N2 6.796 0,790 6.323 6.323 0.52S 1
02 6.216 6.216
H2 0.112 0.112 0.1B2 0.500 0.950
Vopour rraction 1 0 6.387 6.531 1 1 1 1 1 t 1 0 1 0 1 1 1 0 0 U 0 0
Temperature "C 16 i i 15 193 166 186 160 650 180 650 15 650 650 250 40 40 15 15 133 650 40 40 15 30 15 30
Pressure kPo (obs) i5o 1350 1350 1350 1350 1350 1350 1300 1350 1300 1350 1300 1300 1300 1300 1300 2000 150 150 150 150 150 150 150 150 150
MW ko/krrtol 16.0 16.0 18.0 1B.0 17.5 17.5 17.5 17.5 17.5 17.5 28.9 28.9 23.3 23.5 26.9 18.0 28.0 18.0 18.0 10,0 2,8 18.0 18.0 18.0 18.0 16.0
Density 1.03 9.3 999 17.1 12.5 6.57 6.57 2.98 6.57 3.0 16.39 4.87 3.97 7.09 13.60 992 23.7 999 0.B2 0.20 0.16 992 999 995 999 995
CP 0.011 0.011 1.14 _
-
0.013 0.013 0.028 0.013 0.028 0.019 0.045 0.033 0.021 0.018 0.65 0.017 1.1 0.013 0.024 0.0087 0.65 1.1 0.80 1.1 0.80
Thermal Cond. W/m K 6.032 0.033 0.60
-
0.039 0.039 . 0.097 0.639 6.69? 0.026 0.063 6.687 0.051 0.037 6.63 0.025 0.60 0.027 0,18 0.17 0.6J 0.60 0.62 0.60 0.62
Heat Capacity kJ/kg'C
i.ii
2.31 4.05 3.65 3.31 2.26 2.20 2.72 2.20 2.72 1.64 i.ii 1.64 1.49 1.20 4.64 1.04 4.05 1.95 3.51 10.2 4.04 4.05 4,04 4.05 4.04
Enthalpy -2.66 -2.66 -31.la -28.18 -30.85 -28.23 -25.41 -22.78 -2.82 -2.53 -0.03 1.60 -27.14 -30.13 -12.4a -22.48 0.00 -21.41 -17.81 -14.98 -0.93 -20.15 -1259.1 -1254.3 -1591.2 -1585.1
NOTf 1: OXYGEN / AIR DISTRIBUTORREQUIRED
NOTE 7: MULTIPOINT THERMOCOUPLES REQUIRED
NOTE 3: PRESSURE TAPS REQUIRED
NOTE 4: MAIN CORE ELUIDIZATION CAS
NOTE 5: ANNULUS GAS
NOTE 6: HEATEP. DUTIES DONOTINCLUDE HEAT LOSSES
NORAM INTERNALCIRCULATING
FLUIDIZED BEDMEMBRANEREFORMER
PROCESS FLOW
SO SLM CH4 FEED. 100SLM H2. AIRADOmON
SOX SWEEP STEAM DILUTION
B - Z 0B 4 5 - 13 9 6
Figure 4.2: Process flow diagram (direct air addition)
N2 sweep^>
(multiple)
H2 permeate)>
(multiple)
Reactor Exit
G: exit gas filter
A: vessel shell
settled catalyst bed height
E: oxidant distributor
C: membrane panels with sweep
inlet and permeate outlet
B: open ended core draft box
H: external reactor heaters
E: annular distributor
D: main distributor
Figure 4. 3: ICFBMR pilot reactor (dimensions in mm, not to scale
99
E - Secondary feed distributor: Preheated annular gas was distributed to the annular quadrants via
four Vi" (6 mm) OD stainless steel sintered metal plugs (20 um nominal pore rating, Mort
Corporation model 6500-
1
/4-V
/
8-20). A photograph of the assembled main and secondary
distributors is presented in Figure A4.1.3 in Appendix 4.1.
F - Oxidant feed distributor: Preheated air was added to the fluidized zone above the core box
through a VS" (13 mm) OD sintered Hastelloy C276 tube (50 mm long, 2 um nominal pore
rating, Mott Corporation). The oxidant distributor was installed horizontally in the reactor,
perpendicular to the membrane panels. Pressure drop data for the three feed distributors are
presented in Figure A4.1.2 in Appendix 4.1.
G - Exit fdters: Non-permeate reactor gases left the reactor via two tubular metal fdters made
from sintered stainless steel (300 mm long, 38 mm OD, 5 urn nominal pore rating, Mott
Corporation). These fdters ensured that only traces of catalyst solids left the reactor. The filter
pressure drop for a flow of ambient temperature nitrogen is presented in Figure A4.1.27,
Appendix 4.1.
H - Heaters: External heaters were clamped onto the reactor. Initially ceramic fibre heaters were
used. However, these failed during the initial pilot plant run, likely due to oil binders in the
insulation short-circuiting the heating wires. The original ceramic heaters were then replaced by
tubular heaters.
The total internal volume of the reactor shell is 0.045 m
3
. The volume of catalyst required to fill the
reactor to the top of the core draft box is approximately 0.021 m
3
. Detailed mechanical drawings for
the external pressure vessel (Figures A4.1.4 to A4.1.6), internal reactor (Figures A4.1.7 to A4.1.9),
internal preheater (Figure A4.1.10) and core draft box (Figure A4.1.11) are provided in Appendix 4.1.
ICFBMR reactor assembly instructions and installation photographs appear in Appendix 4.2.
A formal hazard and operability study (HAZOP) was conducted on the reactor design and pilot plant
modifications. The reactor and pilot plant were inspected by the MRT and CHBE safety committees
prior to operations.
4.2.3 Memb rane Assemb l y L ay out
Rather than risk damaging the palladium membranes in the initial commissioning runs, dummy
internals were initially installed in the reactor. These internals were made from carbon steel and were
dimensionally similar to the membrane assembly presented in Figures 4.5 and 4.6. However, the
dummy membrane panels were thicker (9.5 mm) than the actual membrane panels (6.3 mm) and had
100
no inter-channel communication slots. A drawing for the dummy internals is presented in Figure
A4.1.26, Appendix 4.1.
After commissioning, the carbon steel internals were removed and replaced with the membrane
assembly. Of the twelve membrane positions in the ICFBMR pilot reactor, membrane panels
occupied six spaces for a total of 0.15 m
2
membrane area, based on panel geometry. The balance of
the membrane spaces were filled with '/i " (6 mm) thick stainless steel dummy plates. It would have
also been possible to install six additional single-sided membranes on two of the reactor walls,
bringing the total possible installed membrane area to 0.41 m
2
, in excess of the 0.35 m
2
initially
estimated to produce the design pure H
2
flow of 100SLM.
Core box
:
4
3
A. Possible membrane positions B. Installed ICFBMR panels
Figure 4.4: Location of membranes in ICFBMR reactor (numbered items are installed membranes as
described in Chapter 2, "X" and "Y" are solid V*" thick stainless steel plates. Possible single-
sided membranes on two core box outside walls are not shown.)
Cold modelling (Chapter 3) experiments clearly showed that communication slots between the
membrane channels are preferred to solid (non-communicating) membrane plates. The membrane
panels in the ICFBMR were assembled with horizontal communication slots between panels, as this
maximized the width of the membrane panels. There were three vertical panel rows in the pilot
reactor, with the six membranes installed in the first and third row. The middle (second) panel row
was filled by a plate of stainless steel with no communication slots. Therefore, channels 1 and 2
101
communicated, and channels 3 and 4 communicated, but the middle plate prevented gas and solid
exchange between channels 2 and 3. In retrospect, it would have been preferable to have also had
communication gaps in the middle panel. Figure 4.4 presents a schematic of the membrane
installation showing the location of the six membrane panels described in Chapter 2.
The three membranes and one dummy panel were connected into a row (Figure A4.1.12) by three
"H" shaped pieces (Figure A4.1.15 in Appendix 4). This formed six communication gaps in the
assembly row, each with dimensions of 57 x 22 mm. The communication gaps accounted for 6.5%of
the total row area, slightly less than the 9%fraction in the cold model tests.
Figure 4.5 presents a plan view of the reactor internals. The flow channels within the core box were
identical (16 mm wide). The minimum gap for solids flow between the core box corner and the vessel
wall was approximately 8 mm, more than 60 times greater than the maximum catalyst particle size
used in the reactor (125 pm), large enough to prevent catalyst bridging (Grace, 1982). The three rows
of vertical membranes were held in place by a series of threaded rods. In order to prevent stainless
steel parts from contacting the palladium membrane surfaces, a thin graphite gasket was inserted
between the membrane and the stainless steel backing strip required to secure the panels. Detailed
drawings of the membrane assembly components are provided in Appendix 4.1 (Figures A4.1.12 to
A4.1.15). An end view photograph of the final membrane assembly prior to installation in the reactor
is presented in Figure 4.6.
Figure 4.5: Plan view of ICFBMR reactor internals
102
Figure 4.6: End view photograph of final membrane assembly
4.2.4 Reac tor I nstrumentation
The reactor instrumentation is summarized in the ICFBMR reactor piping and instrument drawing
(Figure A4.1.19 in Appendix 4.1). The two types of instruments used to monitor the ICFBMR
reactor were:
Thermocouples: Long, type K, multipoint thermocouples were inserted vertically downward into
the reactor from the upper reactor flange in order to measure temperature profiles in the annular
region, reactor core and reactor gas space. See Table A4.1.1 in Appendix 4.1 for full
thermocouple descriptions.
Pressure transducers: The reactor pressure (gauge) was measured in the vent space of the internal
vessel. Differential pressure taps were installed at several points in the reactor. See Table A4.1.2
in Appendix 4.1 for full transducer descriptions. Five sampling points were also placed in the
reactor. Three differential pressure transducers were used (Omega PX-750, 0-2.54m WC). The
sampling line tips were covered with a sintered stainless steel plug (nominal 20 pm, Mott 6500-
1/4-1/8-20) to prevent catalyst entry (see Table A4.1.3 in Appendix 4.1 for locations).
103
Instrument locations within the ICFBMR reactor are summarized in Figure A4.1.20 (Appendix A4.1).
Pressures and temperatures of the external pressure vessel were monitored to ensure that the reactor
operated within its mechanical design limits. Instrument measurements were logged in the control
computer twice per minute.
4.3 Pilot Plant Description
Figure 4.7 presents a process schematic of the pilot plant. The main feeds to the system are
compressed natural gas, deionized water and, if running ATR, compressed air. Table A4.2.4 in
Appendix 4.1 provides a description of the main equipment components. The main process blocks of
the pilot plant included:
Natural gas feed: Natural gas was first compressed to approximately 2,000kPa, then desulfurized
at ambient temperature in an adsorbent bed filled with CuO (8 wt%) impregnated into granulated
activated carbon (Calgon Sulfasorb-8, 4x10 mesh). A typical analysis of the natural gas supply
for the Vancouver area is shown in Table A4.1.5, Appendix 4.1. As the methane content is high
( > 95% ), the natural gas was assumed to be 100%methane for all process calculations.
| Sweep N2^-
from cylinders
jOxidation Air/-
f ro m cylinders
Natural gas^ ( V
frnm mai ns ^
Gas compressor
(C-1)
City water
Desulfurizer
(DSU)
Deionizer
Water
"pump"
(V302A/B)
(DIU)
Water
"pump"
(V302A/B)
Condenser (E-2)
Hydro gen^
to vent / GC
Figure 4.7: Pilot plant schematic
Off-gas ^>
to vent / GC
j Condensate^
to drain
104
Water feed: City water was deionized in a mixed-bed ion exchange system (US Filter, activated
carbon bed followed by two mixed resin beds). The water was then pressurized to approximately
2,000 kPa in V302A/B and metered to a preheat interchanger (E-l).
Reactor feed: Natural gas and steam were mixed, and then preheated in the external electrical
preheater (E-3) and then in an internal electrical preheater (H-l).
Reformer: The natural gas and steam reacted on the fluidized catalyst to produce a reformate
mixture (H
2
, CO, C0
2
, CH 4, H
2
0). The endothermic reaction heat was supplied by external
heaters or by direct air addition to partially oxidize the reactor gases.
Membranes: H
2
permeable membranes removed produced hydrogen directly from the fluidized
bed reformer. An inert sweep gas (N
2]
Praxair industrial grade, >99.995%) could be used to
enhance hydrogen permeation. The combined permeate H
2
flow from the active membranes was
measured with a dry gas meter (American Meter, model AM-250) before being vented to
atmosphere. The permeate H
2
was analyzed in a gas chromatograph ("GC #2" in Table A2.2 in
Appendix 2) by injecting from filled sample bags.
Off-gas treatment: The hot non-permeate reactor gases leaving the reformer were cooled to
ambient temperature and condensate was separated before the off-gas was vented. The off-gas
could also be sent directly to a gas chromatograph for analysis ("GC #1" in Table A2.2 in
Appendix 2).
Piping and instrumentation drawings (PIDs) for the pilot plant are presented in Figures A4.1.16 to
A4.1.18 in Appendix 4.1. The pilot plant was controlled by a programmable logic controller (PLC,
GE Fanuc, series 90-30), which ran both the control loops and the safety shutdown logic. The pilot
plant operator had access to the PLC program through a control computer, which ran a custom-built
program created using commercial HMI (human machine interface) software (Cimplicity). The five
operating screens from the HMI program used to operate the pilot plant are presented in Figures
A4.1.21 through A4.1.25 in Appendix 4.1. The main control variables in the pilot plant were:
Natural gas flow (mass flow controller).
Water flow (measured by a turbine flow meter, flow manually adjusted).
Oxidant air flow (mass flow controller).
Preheat temperature (adjusted by heater input).
Reactor temperature (adjusted by heater input or by air addition).
Reactor pressure (automatic control valve).
105
4.4 Pilot Plant Operation
Detailed operating instructions for the pilot plant are located in Appendix 4.3. The general procedures
to start-up the system are listed below. The shutdown procedure was a reverse of the start-up
procedure.
Start the control computer and PLC.
Open H
2
and N
2
gas cylinder supplies.
Pressurize external shells of preheater and ICFBMR reactor with N
2
.
Fluidize the ICFBMR with N
2
at low pressure (< 300kPa). .
Turn on the process heaters and slowly raise the reactor temperature at a rate of <2C/minute
until the bed reaches 250C.
Introduce H
2
, then raise slowly raise the reactor temperature to 500C at a rate of <3C/minute in
a N
2
/H
2
atmosphere.
If required, hold the reactor at conditions suitable for catalyst reduction.
Set a small flow of water, converted to steam in the feed preheaters, followed by natural gas.
Sample the non-permeate reactor off-gas (ROG) until CO present, indicating CFL reformation.
Shut off H
2
, then stabilize operations at the desired temperature, pressure and feed rate.
Measure permeate flow using a stopwatch and dry gas meter.
Measure permeate purity (GC #2).
4.5 Catalyst
The total catalyst charge in the ICFBMR pilot reactor was 0.021 m
3
, which brought the settled bed
depth just over the top of core box. The free volume in the core box (the volume not occupied by
membranes and dummy panels) was 0.0085 m
3
. It is in this volume that the bulk of the reforming
reaction occurs. The SMR reaction volume (V) increases to 0.0090 m
3
if we include the reactor
volume immediately above the bottom distributor, but below the core box. Under the flowsheet
conditions presented in Figure 4.2, the methane/steam feed has a volumetric flow of 2.8 m
3
/h. If we
assume that a bubble void volume of -20%of the core box volume not available for reaction, an
estimate of the SMR space velocity (s) at the ICFBMR flowsheet operating conditions (1,300 kPa,
650C) can be made:
b
>f
\
m f J
2
-
S m l h 1
=39 0/. " ' (4.2)
0. 0090w
3
0.8
106
The relatively low space velocity in the ICFBMR pilot reactor is a result of the need to accommodate
the hydrogen membranes in a practical layout for fluidization. Commercial NiO catalysts can be
operated at space velocities above 200,000 h"', but conventional fixed-bed SMR reformers operate
with significantly lower space velocities due to heat transfer and mass transfer constraints. Given the
relatively large volume available for reaction in the ICFBMR pilot reactor, it was decided that it
would be acceptable to dilute the active catalyst with alumina to conserve catalyst stock. It should be
noted that ICFBMR operates ~300C colder than the conventional SMR process, and therefore
reaction kinetics will be slower. Two types of catalyst were employed separately in the ICFBMR
pilot plant:
SMR catalyst: A conventional SMR catalyst, Sud Chemie G-91 5/8"x 1/4"EW, was used initially.
The SMR catalyst (18%NiO, 1.6%K
2
0, supported on alumina) was designed for a conventional
fixed bed reformer, and was in the form of spoked cylindrical rings. The catalyst rings were crushed
in a grinder, then lightly fluidized for several days in atmospheric air. The resulting material was then,
sieved to obtain a powder in the particle range of 50 to 125 urn. The crushed SMR catalyst was then
diluted with an equal volume of alumina powder before being introduced into the pilot reactor.
Autothermal reforming (ATR) catalyst: A novel ATR catalyst was prepared by a commercial catalyst
supplier on MRT-suppIied alumina substrate. The catalyst supplier indicated that this ATR catalyst
formulation had been successfully tested for ATR in the form of a fixed-bed monolith, but had not
been previously used in a fluidized bed. By agreement with the catalyst supplier, no chemical
analysis could be undertaken on this ATR material. It is likely that the formulation was based on a
noble metal, such as rhodium, palladium or platinum. See Ayabe et al. (2003) for a discussion of
various noble metal ATR formulations.
In order to produce a fluidizable ATR catalyst, a high-quality y-alumina powder (Alcoa HiQ
7S19CC) was supplied to the catalyst manufacturer for impregnation. Its average particle diameter
was 87 urn (see Figure 3.2 in Chapter 2 for particle size distribution). Before impregnation, the
alumina powder was preconditioned at UBC by lightly fluidizing with air for several days in a
Plexiglas column. The alumina was then screened (+38 urn, -250 um). This preconditioning was an
attempt to remove any fines that might be initially produced by fluidization, but in fact very few fines
were found in the final screening. For the ICFBMR experiments, the ATR catalyst was diluted 9:1 by
the same alumina as had been utilized as the catalyst substrate.
107
Particle size distributions and hydrodynamic characteristics for the two catalysts are summarized in
Chapter 3. Both catalysts can be considered Geldart type A powders. The activity of the catalyst was
tested in a microreactor prior to loading the pilot reactor and after pilot test runs. Appendix A4.4
describes the microreactor system set-up. The microreactor tests did not attempt to obtain intrinsic
kinetic data as their purpose was to check catalyst and compare activity of fresh and used catalyst at
space velocities significantly higher in of the ICFBMR pilot reactor.
4.6 Pilot Plant Experiments without Membranes
A number of experimental reforming runs were conducted in the ICFBMR pilot plant, initially with
dummy steel internals installed, then with palladium membranes. The overall objectives of the
ICFBMR pilot testing were:
Qualitative evaluation of the ICFBMR reactor concept, including reactor stability, reactor
isothermality, catalyst circulation and segregation of nitrogen in the oxidation air from the reactor
core.
Quantification of the reactor performance, including hydrogen recovery and demonstration of an
equilibrium shift.
Evaluation of the planar palladium membranes in a fluidized bed reformer.
The process variables explored in the pilot plant work included:
Reactor pressure and temperature.
Natural gas feed rate.
Steam-to-methane molar feed ratio.
Operation with and without sweep nitrogen.
External heating (SMR) and autothermal operation (ATR) with varying air feed rate.
Table 4.1 summarizes the pilot plant experimental program. No membranes were installed in the first
run, as its purpose was to commission and prove the pilot system. A carbon steel dummy internal was
inserted in the ICFBMR to simulate the membranes, similar to the cold model testing. After the first
run, the carbon steel dummy assembly was replaced by membrane assembly, which remained
installed for the duration of the experimental program. Not all of the data from the pilot runs are
described in this chapter; only results that are believed to give insight into the ICFBMR performance
are presented.
108
Table 4.1: Summary of ICFBMR experimental runs
Run Dates Catalyst Comments Run time (h)
1
July - Sept, 2003 Diluted NiO
Commissioning runs, dummy
internals installed (no membranes)
2
Aug 9-12, 2004 As above
Reactor heaters replaced
Membranes installed
90
3
Sep 20-22, 2004 As above
Heluim tracer study
SMR &ATR testing
65
4
Oct 26-28, 2004 As above Low catalyst activity experienced 65
5
Dec 13-14, 2004
Used ATR (11%)
diluted with alumina
Low catalyst activity experienced 24
6
Aug 18-21,2005
Virgin ATR (10%)
diluted with previous
ATR material
SMR &ATR testing
Up to 650C operation
Low catalyst activity experienced
after -40 hours
90
334
A series of experimental runs was conducted on the ICFBMR pilot plant with dummy internals
installed in the reactor. The specific objectives of these runs were:
To prove operation of the pilot plant, including the PLC control system and ICFBMR heaters at
reforming temperatures and pressures.
To investigate hydrodynamic characteristics, such as bed and distributor pressure drops.
To perform reforming runs on the reactor to confirm catalyst activity and gas chromatography
procedures.
The core draft box of the steel dummy matched the dimensions'of draft box used to house the
membrane internals in subsequent ICFBMR experiments. However, the dummy internals had three
solid (i.e. non-communicating) plates to simulate the membrane surfaces, while the membrane
assembly had horizontal communications slots (Figure 4.4). As discussed in Chapter 3, results from
cold model experimentation indicated that the non-communicating panel design is prone to
maldistribution of solids and gas among core flow channels, leading to flow instability.
The reactor was filled with 21 liters of the diluted NiO catalyst powder mixture (50 wt%SMR
catalyst, balance alumina). The physical properties and fluidization characteristics of the NiO catalyst
mixture are summarized in Table 3.1 in Chapter 3. This batch of catalyst had been previously used in
reforming experiments conducted by MRT. As indicated in Table 4.1, this catalyst mixture was used
for ICFBMR pilot plant runs #1 through #4. The settled catalyst bed depth was confirmed to be 25
109
mm above the top of the core draft box. The catalyst was reduced by fluidizing for four hours in a
30%H
2
, 70%N
2
mixture at 500C and 300kPa. Notable results of the commissioning runs include:
Although the chemical duty of the reforming reaction was modest, the temperature profile within
the reactor core was very uniform (less than ~10C variation).
Overall heat losses from the reactor were found to be -2 kW.
The freeboard of the reactor was about 30-50C colder than the main bed, resulting in reaction
reversal in the freeboard. The gas analysis of the outlet gases therefore tended to show
significantly lower methane conversions than expected based on the main reactor operating
temperature. This phenomenon was present in all of the experimental runs to some degree.
The pressure drop over the two sintered metal outlet filters was stable and acceptable. As a result,
the back-pulsed nitrogen cleaning system was not required.
Several components in the ICFBMR system did not perform as well as expected and had to be
replaced after the commissioning runs:
ICFBMR heaters: After approximately 36 hours of service, the resistance of the four ceramic reactor
heaters (Watlow VS108A30S) dropped by -25%. Their resistance continued to decrease to about
-50%of their original value. At the end of the commissioning runs, the internal ICFBMR was
removed from the pressure shell, and the ceramic heaters were replaced with four new 0.5 kW tubular
heaters (Watlow Incoloy RDN134J10S). It is believed that organic binders present in the insulation
blanket permeated the ceramic heaters, leading to short-circuiting of the heater wires. The ceramic
heaters clamped onto the internal preheater were of design similar to the failed units, but surprisingly
suffered no performance deterioration during the ICFBMR pilot program.
Plugged distributors: The secondary feed distributor initially installed in the ICFBMR incorporated a
ring header with an angled distribution point in each annular quadrant (Figure A4.5.1, Appendix 4.5).
The 0.6-mm diameter holes in the distributor partially plugged with catalyst solids, and the assembly
was then replaced by the sintered metal distributor presented in Figure A4.1.3 in Appendix 4.1.
Similarly, the original orifice air distributor (Figure A4.5.2, Appendix 4.5) also partially plugged with
catalyst solids during commissioning runs, and was replaced by the sintered metal distributor
described in Section 4.2.2. Although orifice distributors are generally preferred for fluidized beds, the
many start-ups and varied gas flows presented opportunities for backsifting, which was prevented by
the sintered metal distributors.
110
Thermocouples: Several of the multipoint thermocouples failed in service, likely a result of the
bending required by the rather complication installation procedure. Disassembly and re-assembly of
the pilot plant reactor was challenging and very time-consuming. As a result, the failed multipoint
thermocouples were not replaced, and temperature profile information from the pilot plant tests was
incomplete.
4.7 Pilot Plant Experiments with Membranes
Although the installation of membranes did not complicate reactor control, the extra flow and gas
analyses added extra operational tasks. Additional upgrades to the pilot control system, such as a
permeate H
2
mass flow meter and an automatic gas chromatograph sampling system, would have
facilitated generation of reliable experimental data.
A mass balance closure around the pilot plant was attempted for several atomic species (carbon and
nitrogen) during a number of the experimental runs, but was not possible for hydrogen and oxygen, as
the condensed water in the reactor off-gas was not measured. The error in the atomic carbon balance
(carbon in - carbon out) was generally within 15%. Although the reactor feed gas flow was known
accurately, the reactor off-gas flow was measured manually with a dry gas meter and stopwatch, and
there was a potential for leaks from the pressurized system.
4.7.1 Membrane Performance
The performance of the H
2
membranes is the key to the ICFBMR system. The three most important
membrane performance parameters are:
Purity - Ultrahigh purity is desirable in order to meet fuel cell specifications.
Flux - Sets the H
2
production rate of the system.
Effectiveness - Defined here as the fraction of measured H
2
flux relative to the predicted
flux, thus a measure of the excess membrane required above theoretical predictions.
4.7.1.1 Membrane Performance
The total cumulative time that the membranes were exposed to hot, fluidized operating conditions in
the pilot reactor was approximately 14 days. The membranes cycled from ambient conditions to hot
temperatures (>500C) six times. As presented in Figure 4.8, the combined hydrogen permeate was
initially found to be "pure"H
2
(>99.999%, excluding N
2
present from sampling or sweeping) until the
cumulative run time was approximately 180 hours, from which point the averaged measured purity of
the combined permeate was 99.8%(dry basis). Given the presence of methane, it is likely that there
were also traces of steam in the permeate H
2
at concentrations of -0. 2% . The times of the six start-
111
ups / shutdowns of the pilot reactor are also shown on Figure 4.8, as are the reactor core operating
temperature (right hand axis). Membrane impurities were detected midway through the third test run,
just after the reactor core was operated at 575C. However, a link between operating temperature and
H
2
purity cannot be concluded. The maximum core operating temperature was 650C, near the end of
the last run.
Table 4.2 summarize permeate testing results for each of the six membranes panels installed in the
reactor. No leaks were detected in four membranes during the pilot testing, and the two leaking
membranes produced relatively high purity hydrogen throughout the entire pilot test.
Table 4.2: Permeate purity (dry basis) from membranes operating in ICFBMR pilot reactor
(excluding N
2
, see Figure 4.4 for location of membranes in the reactor)
Membrane Location Run time to 1
st
detected leak (hours)
Lowest detected
H
2
purity
1 3
rd
from top (right) No impurities detected >99.999%
3 2
nd
from top (right) 253 99.72%
4 Top (right)
No impurities detected >99.999%
5 3
rd
from top (left) 173 99.67%
6 2
nd
from top (left) No impurities detected >99.999%
8 Top (left) No impurities detected >99.999%
4.7.1.2 Membrane Flux Testing
In Table 2.4 (Chapter 2), the effective area of each of the membranes was calculated from permeate
test data. From this, the total permeation area of the six membranes installed in the pilot reactor was
calculated to be 0.060 m
2
. Individual flux testing of the membranes installed in the pilot reactor was
periodically performed at elevated temperature (>500C) under a pure H
2
atmosphere with no N
2
sweep to the membranes, to ensure that the partial pressure of hydrogen in the system was equal to
the absolute pressure. H
2
was fed to the pilot reactor in excess of the membrane flux and above the
minimum fluidization velocity. The effective permeation area of each membrane was calculated
based on the measured flux and Sievert's law permeation equation (equation 4.1). Table 4.3
summarizes the calculated effective area of each of the six membranes during two such tests, as well
as the pre-pilot data from Chapter 2. As previously noted, the expected permeation area of each
membrane based on the panel geometry was calculated to be 0.0258 m
2
(six panel total =0.155 m
2
).
112
100.0
99.8
b 99.6
a
CM 99.4
I
99.2
Combined H2 permeate (left axis)
Startup / Shutdown
A Core temperature (right axis)
A
A \
A A A A A
.->
AAA
/f t
2A
A
650
600 ~
o
3
+>
re
550
E
o
L.
o
500
99.0
50 100 150 200
Run time (hours)
250 300
450
350
Figure 4.8: Purity (dry basis ) of combined hydrogen permeate (excluding N
2
) and core reactor temperature over
the duration of the I CF BMR pilot reactor testing
The data from the reactor flux testing generally gave calculated membrane areas slightly higher than
the pre-reactor permeation testing. The flux data are somewhat inconsistent, especially for panel #8,
but for the most part the relative areas of the membranes are approximately the same within each data
set. It is likely that some of the measured variation is real (i.e. adsorbed surface impurities during the
pre-pilot permeation tests), but experimental error such as temperature variation and gas leaks in
permeation testing equipment probably also contributed to the inconsistency.
Table 4.3: Calculated effective permeation area of the membranes installed in the pilot reactor (see
Tables A4.6.2-3, Appendix 4.6 for data, 0.0258 m
2
is expected permeation area of 1 panel
based on membrane geometry)
Membrane
Average of calculated effective permeation area (m
2
)
Membrane
Pre-pilot testing
(Table 2.4)
After run #5 During run #6
1 0.0121 0.0154 0.0142
3 0.0101 0.0124 0.0118
4 0.0075 0.0102 0.0099
5 0.0142 0.0184 0.0165
6 0.0059 0.0075 0.0064
8 0.0101 0.0113 0.0080
Total 0.0599 0.0752 0.0668
Fraction of
1 0.0258 m
2
38.7% 48.6%
43.2%
4.7.1.3 Flux Under SMR Conditions
The effective membrane area for a number of ICFBMR operating runs is presented in Table A4.6.4,
Sheet3 (Appendix 4.6). The effective membrane area was calculated based on equation 4.1 and the
reactor operating variables for each operating point. The variables needed to calculate the effective
membrane area were:
Temperature - The average reactor core temperature was used.
H2 partial pressure in the permeate:
o Assumed to be 101 kPa for all non-sweep operating points.
o For the N
2
-sweep cases, the H
2
partial pressure was assumed to be 101 kPa multiplied by
the measured H
2
mole fraction of the combined permeate stream, which was typically in
the range of 35 to 50%.
H
2
partial pressure in the reactor:
o For SMR operation (no air addition), the H
2
partial pressure was estimated by calculating
the equilibrium reactor gas composition from the reactor feeds, temperature and pressure
114
at two points within the reactor (inlet and exit, after H
2
permeation). The permeate H
2
partial pressure used for permeation was the average of the two values,
o For ATR operation (air addition to top of reactor), the reactor equilibrium was calculated
as in the SMR case, except that 0
2
was excluded (as it is consumed in the upper reactor,
away from the membranes) and only 10%of the N
2
in the oxidation air was assumed to
reach the core permeation zone, based on results from the cold model work. The balance
of the N
2
in the oxidation air was assumed to not circulate to the reactor core, but rather
to leave the reactor directly.
The average permeation area calculated from the data listed in Table A4.6.4, sheet 3 (Appendix 4.6)
for the case of no sweep gas is 0.075 m
2
, similar to the areas calculated in Table 4.3 based on the pilot
flux tests. This implies that the membrane "efficiency"was close to 100%in the pilot reactor for the
no-sweep operating points.
The average calculated permeation area calculated for cases with sweep nitrogen was lower (0.059
m
2
). This is likely due to the assumed H
2
permeate partial pressure being less than under actual
operating conditions. As the H
2
flux on each panel varied somewhat, the H
2
permeate partial pressure
on any individual membrane would not necessarily be equal to the measured combined H
2
permeate
concentration. In addition, the gas mass transfer resistance on the permeate side of the membrane
means that the H
2
partial pressure will be higher than the permeate gas leaving the membrane panel.
Clearly the N
2
membrane sweep was less than fully effective.
4.7.2 SMR Operation (External Heating Only)
The highest membrane flux was expected for SMR operation at the highest reactor operating
temperature and pressure, with sweep gas fed to the membranes. However, this turned out not to be
the case, as the catalyst activity at the highest core operating temperature (650C) was low. The
maximum recorded H
2
production rate was 17.6 SLM (1.06 Nm
3
/h) at 589C and 1,209 kPa using
nitrogen sweep to the membranes. Table A4.6.4, Appendix 4.6, summarizes the measured hydrogen
flux different operating points.
As discussed above, the measured exit gas composition of the reactor is not a true measure of the gas
composition in the reactor core as the temperature drop in the freeboard reverses the SMR reaction.
The only practical way of estimating the theoretical membrane flux is to assume that the non-
permeate reactor gases are at equilibrium at the reactor temperature and pressure. However, in a
significant number of the data points in Table A4.6.4, the measured methane conversion in the reactor
115
off-gas exceeded the equilibrium methane conversion with no H
2
removal. This is evidence of an
equilibrium shift caused by in-situ H
2
removal.
Experimental data showing the effect of the main process operating variables is now presented. In
some cases the pilot plant results are somewhat sparse, as it proved difficult to operate the pilot
single-handedly. However, in general the reactor performance followed trends suggested by
equilibrium reactor modelling.
4.7.2.1 Effect of Temperature
Increasing temperature increases the H
2
flux by shifting the SMR equilibrium towards products and
by increasing the permeance of the palladium foil. Figure 4.9 presents selected H
2
recovery data as a
function of reactor temperature from run #3, with and without sweep N
2
to the membranes. The
enhancement of H
2
recovery by sweep N
2
is evident. In addition to experimental error, some of the
data scatter is due to the fact that other operating variables (such as reactor pressure, steam-to-carbon
ratio and permeate H
2
partial pressure) could not be controlled to be identical for each operating
point. Nevertheless, both sets of experimental data reasonably follow the predicted trend lines.
1.2
0.4 -I 1 , , , , 1
550 560 570 580 590 600 610
Temperature (C)
Figure 4.9: Permeate hydrogen recovery relative to gas feed rate as function of reactor temperature
and N
2
sweep (run #3, 15 SLM natural gas, reactor pressure ranges from 1,090 to 1,275 kPa,
S:C = 2.1 to 4.0, predicted lines are 15SLM CR,, 2.4 SLM N
2
, S:C = 3.0, 1,200 kPa, permeate
pressure = 101 and 50 kPa for sweep / no-sweep respectively, area = 0.060 m
2
)
Figure 4.10 presents another set of H
2
recovery data as a function of temperature at slightly higher
temperatures. Again, hydrogen recovery increased with temperature, though it should be cautioned
that the catalyst activity for these operating conditions was low. The enhancement of the H
2
recovery
with sweep N
2
is again shown. Figure A4.6.1 (Appendix 4.6) presents the measured and predicted
methane conversion for these operating conditions.
116
1.0
>
o
u
<D
I
o
C N
X
0. 8
0. 6
0. 4
0. 2
0. 0
Imodel for A = 0.06 m2, 50 kPa permeate
X model for A = 0.06 m2, no sweep
A no sweep - measured
sweep - measured
Q
g
A
n
A
A
560 580 640 660 600 620
Temperature (C)
Figure 4. 10: Permeate hydrogen recovery relative to natural gas feed rate as function of reactor
temperature and sweep gas (1, 060 kPa, steam-to-carbon = 3. 0, run #6)
4.7.2.2 Effect of Steam-to-Carbon Ratio
The steam-to-carbon feed ratio was varied in some experimental runs. As shown in Figure 4. 11, the
predicted and measured effect of this variable on H
2
production is modest. It should be noted that the
catalyst activity was again low during these test runs. Although the effect on the H
2
flux is modest,
lower steam-to-carbon ratios tend to improve the thermal efficiency of a SMR system. Figure A4.6.2
(Appendix 4.6) presents the corresponding measured and predicted methane conversions.
0. 7
0.6
0. 5
0. 4
0. 3
0.2
0.1
0. 0
>
o
o
k.
X
O
cvi
I
model for A = 0.06 m2, 50 kPa permeate
model for A = 0.06 m2, no sweep
sweep
A no sweep
2.0 2.5 3.0 3.5 4. 0
Steam-to-carbon molar ratio
Figure 4. 11: Permeate hydrogen recovery relative to natural gas feed rate as function of steam-to-
carbon molar ratio and sweep gas (1, 060 kPa, 570C, run #6)
117
4.7.2.3 Effect of Feed Rate
At very high hydrogen recoveries (> 2V
2
moles H
2
per mole of natural gas feed) the H
2
partial
pressure in a plug flow membrane reactor drops significantly at the reactor exit, decreasing the flux
through the membranes located near the reactor exit (see modelling output in Chapter 6) . However,
at low hydrogen recoveries (less than ~IV
2
moles H
2
per mole of natural gas feed), the H
2
partial
pressure does not decrease significantly with in-situ H
2
removal. This is the situation in the pilot
plant, as the hydrogen flux was found to only decrease marginally at lower feed rates. Figure 4.12
presents all of the Table A4.6.4 hydrogen recovery data as a function of the natural gas feed rate.
There is variation in the data, as there was no attempt to match the operating conditions (e.g.
temperature, pressure, sweep gas), but the trend is clearly to higher H
2
recovery at lower natural gas
feed rates. This figure also highlights that the pilot reactor performance was flux limited. The
installed membrane area governs the H
2
production rate; varying operating conditions only modestly
affects the membrane flux. Figure A4.6.3 (Appendix 4.6) presents the same data, but expressed as the
absolute permeate H
2
flux, showing that this was almost independent of the natural gas feed rate.
1.4 T .
1.2 H
0.0 "I 1 1 1 , , r ~\
10 15 20 25 . 30 35 40 45
Natural gas feed rate (SLM)
Figure 4.12: Hydrogen recovery as a function of natural gas feed rate for all data in Table A4.6.4
The highest measured hydrogen recovery was 1.17 Nm
3
/Nm
3
of feed natural gas (data set #20, Table
A4.6.3, Appendix 4.6). The feed flow of natural gas was 15 SLM for this operating point. Higher
recoveries were anticipated for the high temperature operating points in run #6, but poor catalyst
activity hindered reactor performance.
118
4 . 7. 3 ATR Operation (Air Addition)
A series of ATR experiments were performed to determine the effect of the rate of air addition on
hydrogen production. The reactor was first stabilized under SMR conditions at 1,100 kPa and a core
temperature at ~560C. The natural gas feed was set at 20 SLM and the steam-to-carbon ratio at 3.0
for all test points. Air was then introduced in increments up to a maximum feed oxygen-to-methane
molar ratio (0
2
:CH}) of 0.6. A constant flow of sweep nitrogen was maintained to the membrane
panels. No methane or carbon monoxide impurities were detected in the permeate testing. A summary
of the operating conditions and experimental results are presented in Table A4.6.6, Appendix 4.6.
Figure 4.13 presents the H
2
partial pressure in the reactor predicted by the Gibbs reactor equilibrium
model if the system were well mixed for operating conditions #1-8 in Table A4.6.6, and account for
the measured permeate H
2
removal. As the air addition rate increased, the H
2
partial pressure in the
reactor decreased, reducing the membrane permeation driving force.
250 j
<D
3
225 n
(A
tn
0)
l _ 200 -
Q.
re
0.
175 -
ro o
o . -o
o 150 -
c
t
o
E
150 -
re
o 125 -
i _
CN
X
100 --
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
02 : CH4 Mo l ar Rati o
Figure 4.13: H
2
partial pressure in a well-mixed reactor for ATR experimental conditions predicted
by equilibrium model (560C, 1100 kPa, NG feed 20.1 SLM, S:C = 3.0, sweep N
2
to membranes)
Figure 4.14 presents the measured hydrogen flow as a function of the air addition rate. The measured
flow of permeate H
2
was not significantly affected by air addition. This insensitivity of H
2
flux to air
addition is a key advantage of the ICFBMR configuration. Also plotted on Figure 4.14 is the
predicted H
2
flux for a well-mixed system, based on the H
2
partial pressures from Figure 4.13,
normalized to the measured H
2
flux with no air addition. If the entire system were well mixed, the
lower H
2
concentration in the reactor would reduce the membrane flux by almost 40%. However, the
H
2
permeate flow did not change significantly in the ICFBMR pilot testing, confirming that only a
small portion of the nitrogen in the oxidation air circulated to the reactor core.
119
w
ra
E
CD
Q.
5
o
H
CM
X
12
10
8
6
4
2
0
A H2 flux (measured)
A Predicted H2 flux (no rmalized)
0.0 0.1 0.2 0.5 0.6 0.7 0.3 0.4
02.CH4 Molar Ratio
Figure 4.14: Effect of air addition on Ff
2
flux (measured and predicted for well-mixed reactor,
560C, 1100 kPa, NG feed 20.1 SLM, steam-to-carbon = 3.0, sweep N
2
to membranes)
As the oxidant air flow increased, the reactor heaters were reduced from an initial power of 4.2 kW
(SMR, 0
2
:CH4 = 0) to 0 kW at the highest air addition rate (0
2
:CH
4
= 0.6). Simulations presented in
Chapter 7 show that an 0
2
:CH4 molar ratio in the range of 0.35 to 0.4 should be sufficient for the
reactor to run adiabatically. However, the pilot reactor has significant heat losses, so that adiabatic
0
2
:CH4 ratio would be even higher than 0.6 if commercially viable H
2
recovery ratios could be
achieved in the pilot plant. In any event, the testing did show that the reactor duty, although modest,
could be fully sustained by air addition. Under SMR conditions, the temperature profile within the
reactor core was flat, with a temperature variation of approximately 10C. This increased to ~20C at
the highest air addition rate (see Table A4.6.7, Appendix 4.6 for temperature profiles at different air
addition rates).
Figure 4.15 presents additional test data that again indicate that the hydrogen flux is relatively
insensitive to the air addition rate. It should be noted that it likely that the catalyst activity was
somewhat low during these tests. Nevertheless, the H
2
flux was not reduced significantly with air
addition. Also shown is the significant increase in hydrogen flux when sweep N
2
is used.
120
14
12
1 0
s
W 8
X
6
CN
1
4
sweep
no sweep
0 0.1
0.4 0.5
0.2 0.3
02.CH4 Molar ratio
Figure 4.15: Permeate hydrogen flow (with and without sweep gas) with varying air addition rate
(645C, 1060 kPa, N G feed = 20 S L M , steam-to-carbon = 3, A T R catalyst)
4.7.4 Solids Ci rc ul ati on Tests
Similar to the cold model work presented in Chapter 3, a series of helium tracer experiments was
conducted to investigate internal movement of gas and solids within the reactor. Helium was metered
to the reactor through the main oxidant distributor with a rotameter (Figure A4. 5. 3, Appendix A4.5).
Gas samples were taken from various points in the reactor, then analyzed for their helium
concentration in a gas chromatograph.
Figure 4.16 presents the reactor schematic and sample point locations for the tracer tests. Reactor gas
was directly sampled from the annulus, core and freeboard (Points D, E, H , I in Figure 4.16) and the
reactor outlet. During these tests, the reformer was operated under S MR conditions (no air addition)
at ~595C (core), 1,100 kPa with a natural gas feed rate of 42 S L M and a steam-to-carbon molar ratio
of 3.0. The permeate hydrogen flow (with sweep nitrogen) was measured to be between 16 and 17
S L M (as 100% H
2
) during the helium trials.
Figure 4.17 presents the measured helium concentration and methane conversion at various points
within the reactor (see Table A4.6.1 for data). The measured helium concentrations provide strong
evidence of positive solids circulation. Several points are notable:
The helium concentration in the annulus at mid-height was approximately half the reactor exit
concentration. At the top of annulus, the gas composition would be expected to be similar to the
reactor exit. The fact that the annular helium concentration was lower may result from uneven
mixing of the helium in the upper reactor, or modest stripping due to the secondary feed gas.
121
Oxidant f eed
1,380 kPag
He
Sampl e " D"
in slot 2
Sampl e "I" \
in annulus
Sampl e "E" -
in slot 2
Reactor off-gas
(to G C / vent)
Secondary
feed (4)
Oxidant distributor
Sol id divider
Sol id dummy plate (1 of 2)
Sampl e " H" in slot 3
" Membrane (1 of 6)
Core draft box
-t X h To G C
Permeate H2
Main
f eed
Figure 4.16: ICFBMR helium tracer test schematic
The helium concentration in all of the core samples was 5 to 7% of the helium content at the
reactor exit. The fact that the helium concentration was similar in the top and bottom of the core
strongly suggests that the great majority of helium enters the core from the solids circulated from
the bottom of the annulus, rather than due to axial dispersion from the top of the reactor. The
helium tracer testing in the cold model (Section 3.5.4) did find slightly higher helium
concentrations in the top of the core box, likely due to the cold model sample points being located
122
very close to the top of the core box (90%of core height), whereas the pilot reactor sample points
were located somewhat lower (75%of core height).
Non-permeate off- Annulus (I) Slot 2 bottom (E) Slot 2 top (D) Slot 3 top (H)
gas
Figure 4.17: Measured helium concentration (black bars) and methane conversion (open bars)
from ICFBMR He tracer tests (see Table A4.6.1, Appendix 4.6 for data)
The helium concentrations provide strong evidence of the intended up-the-core, down-the-
annulus solids circulation pattern. If the reactor were running under ATR conditions, the helium
concentration profile suggests that only 5 to 7%of the nitrogen in the oxidation air would be
circulated to the reactor core. This corresponds to findings in the cold model helium tracer tests,
where approximately 10%of the helium fed through the oxidant distributor was found to
circulate to the reactor core (see Section 3.5.4).
The core helium concentration was an average of 12%of the measured mid-height annular
concentration. From this, an estimate of the solids circulation rate can be made using the same
equations as in the cold modelling chapter (Section 3.5.4.1). Assuming that the entire reactor feed
flows up the reactor core (42 SLM natural gas, 126 SLM steam), the following estimates of
various reactor hydrodynamic parameters were obtained (see Table A4.6.5, Appendix 4.6 for
calculation details):
Core superficial velocity (U
core
) = 0.18 m/s
Solids circulation rate (m
p core
)= 0.22 kg/s
Solids flux up core (G
pcore
) = 45 kg/m
2
s
Downward velocity of solids in annulus = 0.027 m/s
123
Predictive scaling correlations were developed for the solids flux (positive when flux upwards)
for both horizontally and vertically slotted panels in the cold model testing presented in Chapter 3
(Figure 3.20):
Vertically slotted panels G
pcore
= -1.03E-4(t/
core
p
p
f + 0.180(/
c ore
p
p
) -11.3 (5.1)
Horizontally slotted panels G
pcore
= -4.14E-5(<7
core
p
p
f + 0.083(<7
core
p
p
) +0.65 (5.2)
From the calculated value of U
cart
, (0.18 m/s) and the catalyst particle density (2,150 kg/m
3
), the
predicted solids fluxes (G
pcore
) are 42 and 28 kg/m
2
s for vertically and horizontally slotted panels
respectively, close to the estimate obtained from the experimental data (45 kg/m
2
s). The pilot
plant membrane assembly most closely matches the horizontally slotted panels in the cold model.
Although this is but one data point, the result suggests that the cold modelling results can be used
for hydrodynamic evaluations of the hot, pressurized system.
The measured methane conversion from the in-bed samples was significantly higher than
measured in the reactor off-gas. As discussed above, the reactor freeboard operates cooler than
the main reactor due to heat losses, causing a reverse shift in the equilibrium. Gas analyses are
presented in Table A4.6.1 (Appendix 4.6). The highest measured conversion was in the annulus,
adjacent to the heated reactor wall, as this was the hottest part of the reactor. Table 4.4 presents
the calculated equilibrium temperature needed to match the measured methane conversion at each
point, given the species composition measured by the gas chromatograph. Except for the non-
permeate reactor off-gas sample, the predicted equilibrium temperatures are reasonably close to
what was measured in the reactor.
Table 4.4: Local measured and corresponding equilibrium temperatures
Sample location Temperature (C) Sample location
Measured Equilibrium predicted
from gas analysis
Reactor off-gas (freeboard 579 597
Point I (annulus) 628 621
Point E (bottom slot 2) 593 589
Point D (top slot 2) 595 597
Point H (top slot 3) 590 583
4.8 Catalyst Testing
The catalyst used in the reformer was also tested in a microreactor to its confirm activity. The test
conditions were not in the kinetically controlled region; rather the test conditions were chosen to
124
permit comparison to previous catalyst testing performed by MRT. The tests allowed the relative
activity of the catalyst materials before and after use in the pilot reformer to be ascertained.
4.8.1 S M R Cataly st Testi ng
As indicated earlier, the NiO on alumina catalyst is designed for SMR conditions (no oxidant
addition), and it was not unexpected that the catalyst deactivated after prolonged exposure to ATR
conditions. Figure 4.18 summarizes catalyst microreactor testing under SMR conditions of fresh
catalyst before ICFBMR service, and the SMR catalyst removed from the ICFBMR reactor after the
first and third runs (see Table A4.7.1, Appendix 4.7 for data). The fresh and first-run catalysts show
near-equilibrium conversion. The reason for the initial conversion being slightly above equilibrium
and the slow decline in conversion of the fresh catalyst is not known, but is likely attributable to
small variations in the microreactor temperature.
The catalyst performance after the last SMR catalyst run (run #4 in Table 4.1) clearly shows
declining activity, confirming pilot plant observations. Some residual activity exists, but clearly the
catalyst is no longer useable.
100 -, 1
0 4- , , r ; 1 1
0 25 50 75 100 125 150
Time on stream (h)
Figure 4.18: CFLt conversion in microreactor with NiO catalyst (0.3 g of 50%NiO catalyst and 50%
alumina, 550C and 201 kPa, CFL, feed = 30 Nml/min, H
2
feed = 30 Nml/min, steam-to-carbon
ratio = 3.5, space velocity at inlet conditions = 99,400 h"
1
)
4.8.1.1SMR Catalyst Characterization with TGA and XRD Analysis
When operating the ICFBMR in ATR mode, the catalyst is cycled through oxidizing and reducing
zones. Although the fluidized bed dissipates heat much more quickly than fixed beds, the oxidation
125
zone still exposes the catalyst to elevated temperatures near the air distributor for brief periods of
time. The causes for deactivation of NiO in ATR service have been attributed to nickel oxidation,
carbon formation, sintering and spinel formation (Tomishige et al., 2004). In an attempt to determine
the mode of deactivation for the SMR catalyst, thermo-gravimetric analysis (TGA) and X-ray
diffraction (XRD) analyses of the spent catalyst were undertaken.
TGA analyses of the SMR catalyst are presented in Appendix 4.8. Catalyst samples (~18 mg) were
heated in an air/nitrogen mixture from ambient temperature to 800C, with the sample mass
continually measured. This technique detects sample loss or gain due to oxidation or volatilization.
The fresh catalyst lost almost 4%of its weight, perhaps due to moisture and residual volatiles. The
spent catalyst samples showed no significant weight change, indicating that there were no large
deposits of carbon. However, it should be noted that the spent catalyst had a grey-black appearance,
and small traces of carbon may have been present, below the detection limit of the TGA system used
(< -0.25%).
XRD analyses of several SMR catalyst samples are presented in Appendix 4.9. There were no
significant differences in the spectra from fresh and spent catalyst, suggesting that spinel formation
was not significant.
4.8.2 A T R Cataly st Testing
Two ICFBMR runs were carried out with the novel ATR catalyst from a large commercial supplier.
The first run used a mix of previously-used ATR diluted with alumina. The second ATR run used a
mix of virgin ATR blended with bed material from a previous run. Low catalytic activity was
experienced in both runs, resulting in disappointing reactor performance.
The activity of the virgin ATR catalyst (diluted 50%with alumina) was tested in a microreactor under
ATR and SMR conditions (Figure 4.19, data in Table A4.7.2 in Appendix 4.7). The space velocity of
the catalyst was 12,000 h"
1
under SMR conditions. The methane and steam flow to the reactor were
kept constant during the various operating modes. Air was used in the ATR mode. Alternating SMR
and ATR operating conditions were also tested by cycling the air on for one minute, then off for one
minute over a 45-minute period (see "0
2
cycling" in Figure 4.19).
The catalyst activity was relatively stable over the 100-hour test run. There is some variation in the
data, especially the initial "ATR" run, likely attributable to deviations of the microreactor
temperature from 550C. As the space velocities in these tests were relatively low, the measured
126
methane conversions were close to equilibrium values (see Table 4.5), except for the last "ATR" run,
where the measured methane conversion was slightly lower.
80 -, - I
I - B- 2. S MR With H2
O ! A 3.SMR Without H2
j X 4.02 Cycling
I A 5.ATR
20 -I , : , : ; , 1
0 30 60 90 120
Run time (hours)
Figure 4.19: CFL, conversion in microreactor with virgin ATR catalyst (mix of 0.3 g ATR catalyst and
0.3 g alumina at 550C and 200 kPa, space velocity = 12,000 h"
1
under "SMR" conditions,
steam-to-carbon = 3.5 and CH
4
feed = 60 Nml/min for all tests, "ATR" used air addition with
0
2
:CFL, molar feed ratio = 0.36, all tests except "SMR without H
2
" used H
2
:CH
4
molar feed
ratio =1.0)
Table 4.5: Equilibrium methane conversions for Figure 4.19
(equilibrium conversions are calculated at average measured bed temperature)
Test Description Equilibrium
CH
4
conversion
Measured C T
4
conversion
Test Description Equilibrium
CH
4
conversion Average Std.
Deviation
ATR 57.6% 58.6% 3.8
SMR with H
2
41.1% 42.2% 0.96
SMR without H
2
53.1% 53.9% 0.11
0
2
cycling (same as data #2) 41.1% 39.8% 0.75
ATR (similar conditions as data #1) 55.1% 48.7% 0.29
As discussed above, the catalytic properties of the ATR bed materials in the ICFBMR pilot plant
were poor. This was confirmed in post-run microreactor testing of the bed materials. Both the used
and virgin ATR catalyst mixtures (1
st
and 2
nd
samples respectively in Figure 4.20) showed extremely
low reforming activity. The methane conversion measured during ATR operation is due to reaction of
methane with oxygen. The cause of the loss in catalytic activity is not known, and as the material was
subject to a non-analysis agreement, further testing of the used ATR catalyst was not performed. The
127
catalyst supplier has indicated that this catalyst formulation has been proven to be stable in the form
of an impregnated monolith under both SMR and ATR conditions.
50
40
' 30
>
C
o
o
T t
X
o
20 H
10
1st sample - ATR
- A - 1st sample - SMR
- - 2 nd sample - ATR
-B-2 nd sample - SMR
10 20
Run time (hours)
30
Figure 4.20: Microreactor testing of diluted ATR catalyst after use in ICFBMR pilot plant ("1
st
sample"is used ATR mixture, "2
nd
sample"is virgin ATR mixture, 1.65 g of catalyst mixture at
550C and 200 kPa, space velocity = 12,000 h'
1
under "SMR" conditions, steamxarbon = 3.5,
CFLt feed = 30 Nml/min, H
2
:CH
4
molar feed ratio = 1.0 for all tests, "ATR" used air addition
with 02:CH4 molar feed ratio = 0.5)
The composition of the ATR is not known, but it is possible that it contained rhodium (Rh), as this is
the most common precious metal reforming catalyst described in the literature. Instability of Rh-
catalysts in membrane (Kurungot and Yamaguchi, 2004) and non-membrane reformers (Watson and
Daly) have been described. Sintering of the dispersed Rh particles due to thermal instability of the
catalyst substrate (alumina, ceria and others) is main cause attributed to the Rh deactivation. Perhaps
the y-alumina provided to the ATR catalyst supplier for impregnation was not stable at the elevated
temperatures present in the oxidation zone, but we are unable to draw definitive conclusions without
analysis of the material. In addition to this instability, Beurden et al. also identify the high cost of Rh-
based catalysts as a barrier to commercialization of membrane reformers. Perhaps a more economic
alternative to Rh can be developed, such as bimetallic catalysts based on Ni modified with small
amounts of Pd, Pt or Rh (Mukainakano, 2007).
4.9 Discussion
The membrane area installed in the reactor limited reactor performance, and only a fraction of the
nominal H
2
design capacity was achieved. However, the H
2
production could be reasonably predicted
using a simple equilibrium model coupled with the membrane permeation equation, so it is likely that
128
the design production rate could be achieved if sufficient membrane area were to be installed. The
effect of the main process variables (temperature, pressure, steam-to-carbon ratio, N
2
sweep)
generally followed model predictions.
The permeate H
2
production was relatively insensitive to the natural gas feed rate, as the flux was set
by the limited membrane area in the reactor. As a direct result, the highest hydrogen recovery was
achieved at the lowest natural gas feed rates. This is characteristic of membrane reactors, and
highlights how the reactor performance is overwhelmingly governed by permeation. Only through
increasing the permeation capacity, either by increasing area or decreasing foil thickness, can H
2
production be significantly increased.
The H
2
flux increased significantly when a N
2
membrane sweep was used as it decreased the H
2
partial pressure on the backside of the membrane. Use of an inert gas such as nitrogen for membrane
sweep is not practical for a commercial unit, as an impure hydrogen product would be produced. Use
of sweep steam, as was originally intended for the pilot tests, would be possible as it can be
condensed from the permeate stream. Residual moisture in the H
2
product is acceptable for some
applications such as fuel cells. However, there is a significant energy penalty with use of sweep
steam, and the overall thermal efficiency of the system would suffer. In addition, the water from
which the sweep steam is generated would have to be of extremely high quality, as trace impurities
would end up in the product hydrogen.
Another method of decreasing the H
2
partial pressure in the permeate stream is to lower the absolute
pressure with a vacuum pump. This has been used successfully in pilot tests at both MRT and Tokyo
Gas (Klassen, 2005). It theoretically introduces no impurities into the permeate hydrogen. There are
obvious safety issues with vacuum operation, as there is an inherent risk of air ingress into the
permeate line, posing an explosion risk. This was of special concern here, as the permeate stream
would have to pass through a vacuum pump, a potential source of ignition. Air ingress would also
affect product quality.
The permeability of the membranes did not decrease during the pilot testing. Another important
finding is that the measured permeation fluxes during the pilot reforming tests were reasonably close
to the predicted value, indicating that "effectiveness"of the membrane was close to 100%and
suggesting that the mass transfer resistance within the fluidized bed was low. Value of less than.
100%may be due to:
Mass transfer resistance of hydrogen on the reactor side of the membrane.
129
If using an inert sweep gas, mass transfer resistance on the permeate side.
Pressure drop in the permeate system, so that the absolute pressure on the backside of the
membrane is higher than the measured pressure at the outlet.
Fouling, sintering or other degradation of the palladium foil.
Low catalyst activity.
The calculated membrane effectiveness was close to 100%in the pilot tests, higher than compared to
the work of Adris (1994). Perhaps the flow channels in the membrane assemble contributes to near
plug-flow conditions, reducing axial dispersion and enhancing bed-to-membrane mass transfer. It is
difficult to project whether the membrane effectiveness would decrease if the membrane flux and FL.
recovery were increased to economically practical values. Further experimentation is needed.
Theoretically, dense Pd membranes produce ultra-high purity H2. Given the tight feed specifications
of fuel cell manufacturers, this is a very attractive feature of membrane reactors. Although the H
2
quality decreased to -99.8%midway through the pilot tests, high-purity product was initially
produced, and there were no catastrophic membrane failures, even when the temperature was
increased to 650C. This shows the potential of the uncovered planar membrane to withstand the
fluidized bed environment, but more work is needed to show longevity over months of operation and
to establish a practical upper operating temperature.
Low catalyst activity resulted in poor results for some experimental runs. The deactivation of the
SMR (NiO on alumina) catalyst was not unexpected, as this catalyst is not designed for autothermal
reforming. However, the poor performance of the ATR catalyst was a surprise, and limited the extent
of autothermal reactor testing. No conclusive reasons for catalyst deactivation were found. More
discussions with the ATR catalyst supplier and further testing are needed to better understand the
catalyst performance. One advantage of fluidized beds is that catalyst can be replaced on-line, but this
was not practical with our pilot reactor configuration.
Finally, note that the while the mechanical design of pilot reactor allowed economical carbon steel to
be used for the pressure shell, the complicated geometry was impractical for research purposes. A
simpler, smaller reactor using higher-quality materials may have been more expensive, but would
have greatly helped experimentation. Other areas of the reactor design that could be improved
include:
Reactor connections - There were a very large number of connections to the reactor, especially
on the top flange, primarily for membranes and instrumentation. A change in the membrane
130
design, for example increasing the membrane panel height or eliminating membrane sweep,
would reduce the number of connections and simplify reactor assembly.
Membrane access - The core assembly was housed in a rectangular core box, which hung from
the top reactor flange. Assembly of the core internals was very time consuming. A mechanical
design that would allow improved access to the membranes would be desirable. An alternative
reactor geometry is proposed in Figure 4.21. It uses the chord layout proposed in Figure 3.22
(Chapter 3), in which the catalyst solids return to the bottom of the reactor via two chord
segments, rather than via an annulus. Membranes could then be access through flanges on the
side of the cylindrical reactor. Another benefit is that the membranes would then occupy a greater
fraction of the reactor volume, reducing the overall size of the reformer vessel.
Oxidation air Reactor off-gas
Top of core divider
Membranes
NG / steam feed
Catalyst returns (2)
Membrane flanges
Bottom of core divider
Figure 4.21: Alternate ICFBMR reactor layout (elevation and plan view)
131
4.10 Conclusions
Although operation of the pilot plant proved to be challenging due the scale of the equipment, and
lack of automation, sufficient results were obtained to validate the main features of the ICFBMR
configuration. Conclusions from the pilot testing include:
The uncovered membrane panels withstood ~14 days of hot operation and six temperature cycles
with no catastrophic failures. The permeate hydrogen was initially very pure (>99.999%,
excluding N
2
), but dropped to 99.8%(dry basis) after approximately 180 hours of testing. Four of
six membrane panels did not exhibit any measurable leakage during the pilot tests. Membrane
longevity in hot fluidized bed environments requires further study.
The permeability of the membranes was not significantly affected by pilot testing.
The membrane "effectiveness" was close to 100%in the reforming experiments when no
nitrogen sweep was used. The effectiveness of the N
2
sweep was slightly lower than predicted by
modelling.
Solids were shown to circulate within the reactor at a rate close to that predicted by cold model
scaling correlations.
Air addition had only a modest impact on membrane flux, confirming cold model testing that
showed that only a portion of the N
2
in the oxidation air circulated to the reactor core.
A positive shift in the equilibrium due to in-situ H
2
removal was demonstrated.
132
Chapter 5. Post-Run Membrane Testing
The ICFBMR pilot reactor was disassembled after the experimental runs described in the
previous chapter. The six membranes were removed from the internal reactor assembly,
inspected for damage and tested for leaks. Two of the membrane panels were placed in a
permeation vessel and flux tested. The results showed that the membrane flux was slightly
higher than measured before those membranes were installed in the pilot reactor.
Permeate purity testing on these membranes indicated small leaks, though measured
hydrogen separation factors were still very high. The membrane foil of one membrane was
removed from its stainless steel substrate. SEM-EDX analyses indicated significant scaling
on the backside of the membrane foil, likely the cause of the lower-than-expected
permeation flux of the ICFBMR panels.
5.1 Membrane Removal and Observations
After the pilot tests, the core draft box containing the membrane assembly was removed from the
pilot reactor together with the top reactor flange. Figure 5.1presents a photograph of the I CF BMR
internals being removed from the reactor. Note the grey catalyst scale on all surfaces. A large lump of
catalyst was found adhering to the reactor outlet filters, but this did not totally block the filter
surfaces, and was easy to remove. The outlet filter pressure drop was acceptable during all pilot plant
runs (<100 kPa). No other significant lumps of catalyst were observed on any other internal surfaces.
A l l installed parts were still firmly attached, and no degradation of any components could be seen.
Threaded nuts could be unbolted normally.
The pass-through connections on the top flange (i.e. thermocouples, pressure taps, sweep gas lines,
hydrogen permeate) were removed or cut, and the core box was disconnected from the top flange.
Next the membrane assembly was removed from the core box by first disconnecting the rods securing
the assembly to the box, then by pushing the assembly out of the top of the core box. The assembly
was firmly stuck in the core box, and was removed by knocking the bottom of the assembly with a
heavy hammer.
133
Figure 5.1: ICFBMR internals being removed from horizontal pilot plant reactor
The internal membrane assembly held up well, with all clips, wires, gaskets and nuts still firmly in
place. All metal surfaces were covered with a uniform grey scale, with the exception of half of one
side of membrane panel #8, which was relatively clear. Figure 5.2 shows a photograph of the internal
assembly prior to it being dismantled.
The six membrane panels were removed from the membrane assembly, and then individually leak
tested using the refrigerant detection procedure described in Chapter 2. Significant leaks were
detected on membranes #1, 3, 4 and 5, but not always on both faces of the panel. A possible leak was
found on panel #8. No leaks were found on the membrane surfaces of panel #6. In addition, a small
leak was found on the permeate tube weld on panels #1 and 8. Figure A5.1 in Appendix 5
summarizes the membrane observations and refrigerant leak detection results.
134
Figure 5.2: ICFBMR membrane assembly after service in pilot plant reactor
5.2 Membrane Flux Testing
Panels #6 and 8, thought to be leak-free from the refrigerant check, were flux-tested in the membrane
permeation rig shown in Figure 2.12. Panel #8 was installed at the top of the core draft box, while
panel #6 was located immediately below (see Figure 5.2 above). The permeation vessel contained
pure hydrogen and was heated to 560C. The vessel pressure was varied between 170 and 585 kPa,
and the flux on the two panels measured. The permeate pressure was 101kPa, and no sweep gas was
used. Figure 5.3 presents the resulting flux data as a function of the difference of the square root
hydrogen partial pressures (see Table A5.1 in Appendix 5 for data). The data in Figure 5.3 are very
linear, and the trend line passes near the origin, as would be expected if the hydrogen permeation
followed Sievert's equation.
The membrane panel permeation area was previously calculated to be 0.0258 m
2
from geometry.
Based on membrane permeation equation 2.10, the effective permeation area of the two panels, were
found to be 0.0081 and 0.0167 m
2
for membrane #6 and 8 respectively. These values are significantly
135
higher than previously determined in flux testing prior to the membranes being installed in the pilot
reactor and pilot reactor flux testing (see Table 5.1). The data for panel #8 is especially inconsistent.
0. 004
(A
15 0. 003
0. 002
5
o
0J
-4-
CO
I 0. 001
0 .
R
2
= 0. 9987 ...
x Panel #8
- Panel #6
_
" " '
R
2
= 0. 9995
0 100 200 300 400 500
Partial H2 pressure, hi gh
A
0.5 - Partial H2 pressure, l ow
A
0.5 ( Pa
A
0.5)
Figure 5.3: Post-pilot run flux test data for membrane panels #6 and #8 at 560C
Table 5.1: Calculated effective membrane permeation area, before, during and after pilot runs
Panel Pre-pilot testing Average of pilot flux Post-pilot testing
testing in run 5 and 6
Effective Fraction of Effective Fraction of Effective Fraction of
area (m
2
) expected area (m
2
) expected area (m
2
) expected
#6 0.0059 23% 0.0069 27% 0.0081 31%
#8 0.0101 39% 0.0096 37% 0.0167 65%
The increases in the calculated effective permeation area are not due to membrane leaks, which were
found to be small (see next section). The low initial membrane permeation rate may have been due to
organic impurities initially adsorbed onto the membrane surface, later removed during the ICFBMR
pilot tests. It is not likely that wear of the palladium foil by particle fluidization thinned the
membrane, as a heavy catalyst scale was present on the membrane surface. Subsequent to the pilot
testing, it was found that exposure of the membrane to air at high temperatures (>500C) can oxidize
organic contaminants, restoring the membrane flux (Li, 2005). Another possible explanation for the
higher flux in the post-pilot tests is that surface catalyst scale may have been dislodged during
removal of the membrane assembly from the reactor.
5.3 Permeate Purity
The purity of the permeate gas from panel #6 and 8 was also tested. An equimolar mixture of
hydrogen and helium was fed to the permeation rig (Figure 2.12 in Chapter 2). The rig was then held
136
at the same temperature (560C) as in the flux test described in the previous section. The purity of the
permeate hydrogen was measured with a gas chromatograph, which detected small amounts of
helium in the permeate stream from both panels, indicating pinhole leaks. Table 5.2 summarizes the
permeate purity data, in which the hydrogen-to-helium separation factors are calculated from:
H
2
: He separation factor = {^"/[p _ p jj^
PHeh
~ ^J/j j (5-1)
Equation 5.1 is simply a ratio of the flux to partial pressure driving force for the two species. The
partial pressure difference, rather than the difference in the square root partial pressures, is used as
this permits comparison with microporous membranes. It should be noted that helium has a very
small atomic radius, and thus leaks of heavier compounds such as methane and carbon monoxide
should be lower than for helium. The concentrations of helium in the permeate stream are still low,
and thus did not significantly affect the analysis of hydrogen flux data presented in the previous
section.
Table 5.2: Permeate purity in post-pilot runs
(560C, 50:50 mixture of H
2
and He in permeation vessel, 101kPa permeate pressure)
Panel Vessel pressure (kPa) [He] in permeate H
2
:He separation factor
#6 439 0.031% 6071
#6 439 0.029% 6360
#6 439 0.028% 6525
#8 494 0.25% 671
#8 494 0.26% 660
Gas chromatograph analyses from membrane panels #6 and #8 during the last pilot test did not
indicate any non-hydrogen species. It is not known whether the leaks found during the above post-run
testing were present during the pilot work. They could have been a result of the heavy handling
required to remove the membrane assembly from the ICFBMR core box. >
5.4 Foil analysis with S EM / EDX
The palladium alloy foil from membrane panel #1 (side A) was removed from the stainless steel
substrate by peeling off one corner using a knife. The foil was bonded firmly to the sealing edges, but
could be removed with a firm tug. The permeation area, which was covered by alumina, also
appeared to be bonded to the foil, though more loosely than the seal edges. Figure 5.4 shows a corner
of the membrane foil peeled away, exposing the alumina substrate. The scale on the front of the
membrane could be readily brushed off with tissue paper.
137
Figure 5.4: Peeling of the palladium alloy foil from membrane panel #1
Three samples were cut from the palladium foil and analysed by a scanning electron microscope
(S EM) and ED X (energy dispersive x-ray) using a Hitac hi model S-2300 analyzer. S EM photographs
of the used palladium alloy foi l were taken at x300 (Figures 5.5 to 5.8), xlOOO (Figures 5.9 and
Figures A5. 2, A5. 3 and A5. 5 in Appendi x 5) and x3000 magnification (Figures A5. 4, A5. 6 and A5. 7
in Appendix 5). S EM images of fresh, unused P d
7 5
A g2 5 foil are also presented:
Fresh palladium alloy foi l - Note the smooth surface appearance in Figure 5.5 compared to the
subsequent images of the used foi l . The scratch-like marks may be due to c old rolling
imperfections.
Scaled front (retentate side) - S EM images show heavy scale deposits across the entire
membrane surface (Figure 5.6).
Polished front, exposing metallic foil (retentate side) - The surface morphology is much more
regular than the previous scaled image, but smaller scale deposits are still present on the surface
(Figure 5.7).
Back of membrane (permeate side) - Heavy, irregular deposits are interspersed with smoother,
metallic surfaces, covering approximately two-thirds of the surface area (Figure 5.8).
138
Figure 5.5: S EM of fresh Pd75Ag
2
5 foi l at x300 magnification
X 3Q 0 0000 2 0 1 0 0 P m
Figure 5.7: SEM of polished membrane foil (front) at x300 magnification
;
Is' if* ;
11
.* SSRrf v-SSC^Wt
- -. - > - , - : :
x30 0000 20NV 100^m
Figure 5.8: SEM of back of membrane foil at x300 magnification
14 0
The SEM image in Figure 5.9 is a xlOOO magnification of the back of the membrane foil. Two
distinct surface zones are readily apparent. The rectangular boxes indicate areas where separate EDX
scans were taken.
Figure 5.9: SEM of back of membrane foil at xlOOO magnification
Box 1 and 2 are areas of EDX scan #3 and #4 respectively
Data from four EDX scans of the used membrane are presented in Figure 5.10 below. Metal
concentrations varied considerably in the four zones analyzed.
Scan #1 - scaled front of membrane (Figure A5.8 in Appendix 5): It is apparent that most of the
scale on the front of the membrane is due to nickel, and to a lesser extent alumina, present in the
SMR catalyst. Very little palladium was detected.
Scan #2 - polished front of membrane (Figure A5.9 in Appendix 5): The surface of the foil is
detected in this scan, as evidenced by the large concentrations of palladium and silver. The
measured palladium to silver ratio is approximately 2. Significant amounts of nickel are present,
likely resulting from incomplete removal of the surface scale.
Scan #3 - smooth zone of back of membrane (box 1 in Figure 5.9, EDX scan in Figure A5.10 in
Appendix 5): This area is clearly the metallic foil area of the membrane. Some iron was also
detected, likely from the underlying stainless steel support. Note that almost equal amounts of
141
silver and palladium were detected, a much higher proportion of Ag than detected in scan #2
(polished front) or present in the original foil (25%). This is consistent with other research (Shu et
al., 1993, Amandusson et al., 2001) that indicates silver migration to the permeate membrane
surface. This has been explained as either a thermally induced process to minimize the free
energy of the surface, or induced by surface chemisorption.
Scan #4 - scaled zone of back of membrane (box 2 in Figure 5.9, EDX scan in Figure A5.11 in
Appendix 5): This area contained significant amounts of iron, nickel and chromium, with the
stainless steel sintered support being the obvious source. Palladium concentrations were also
high. Silver was detected, but at lower concentrations relative to palladium than in the original
foil.
1.Front (scaled) 2.Front (polished) 3.Back (smooth zone) 4.Back (scaled zone)
Figure 5.10: Summary of EDX analyses of used membrane foil removed from membrane #1
5.5 Discussion
All six of the membranes removed from the ICFBMR pilot plant appear to have developed leaks,
though it is not known whether all leaks can be attributed to service in the reformer (some may have
been caused by the rough handling required to. dissemble the reactor). From pilot plant results and
post-run permeation tests, it appears that there were no catastrophic membrane failures. Permeate
concentrations of non-hydrogen species were low. Instead, very small pinholes are likely to have
developed, though no pinholes were detected in the SEM scans of the used membranes.
Flux testing on two membranes indicated that permeation was greater after service in the pilot plant,
perhaps attributable to removable impurities, such as carbon, being initially present. It appears that
142
the heavy catalyst scale formed on the membrane surface did not significantly hinder permeation. The
hydrogen flux of the used membranes could be well described with a hydrogen partial pressure
exponent () of V i , indicating that diffusion of atomic hydrogen likely remained the main resistance to
hydrogen permeation.
SEM images of the backside of the membrane indicates the presence of a heavy metallic scale, likely
due to direct contact of the palladium foil with the stainless steel support. The alumina inter-layer
deposited on the sintered metal support was intended to prevent this. The metallic scale covered a
significant portion of the foil, roughly two-thirds in the SEM images. It is likely that this is the main
contributor to a reduction in the membrane permeation relative to that predicted by the Sievert's
permeation equation. The membrane foil may be only releasing hydrogen at the unsealed surface,
thus greatly reducing the effective membrane area. It is concluded that calculation of an effective
membrane area for each membrane, as in Chapter 2, is an appropriate means of characterizing the
loss in permeation.
The mode of pinhole development in the membranes is not known. Perhaps the adhesion of the
metallic scale to the backside of the membrane reduced the foil mobility and led to local stresses in
the palladium as it expanded and swelled with hydrogen and thermal expansion. What is clear is that
the very thin alumina layer deposited below the foil was inadequate to prevent contact between the
palladium and the stainless steel support. Since the ICFBMR membranes were fabricated, MRT has
increased the thickness and modified the composition of the alumina layer, and this has resulted in
membrane permeation areas remaining close to that expected from the geometry (Li, 2005).
143
Chapter 6. Process Simulation and Economics
A commercial process simulator was used to model the ICFBMR reactor and perform a
sensitivity analysis on the major reactor variables. The reactor model accounted for the
internal circulation of solids and gas, but did not include reaction kinetics or
hydrodynamics. A base case model was created for a unit producing 30 Nm
3
/h of high-
purity H2, which was then developed into a process flowdiagram. Performance parameters
and economics of the 30 Nm
3
/h unit are discussed.
6. 1 Introduction
The I CF B M R pilot plant results demonstrated the potential to produce high-purity H
2
, but hydrogen
recoveries were l ow due to the installed membrane area and, in some runs, poor catalyst performance.
In order to extrapolate pilot plant experience to a c ommerc ial design for small-scale hydrogen
production, process simulations were undertaken. The main objective was to create a design tool for
future reactor and process designs. The simulation was also used to reconcile data from the I CF B M R
pilot plant.
F ol l owi ng the experimental F B M R work of Adri s (1994) and R oy (1998), several reactor models
have been developed to simulate the F B M R process using two-phase fluidized bed reactor models:
Adris and co-workers (1997a, 1997b) presented findings from a fluidized bed reactor model,
identifying effects of permeation rate and pressure on methane conversion and hydrogen
production.
Model l i ng by Roy et al. (1998) studied various means of supplying heat to the F B M R process
and concluded that the new process had the potential to reduce capital and operating costs
compared to conventional S M R fixed bed reactors.
Ab b a et al. (2003) adapted a generalized fluidized bed reactor model to autothermal reforming in
a F B M R . Results indicated a significant reduction (-30%) in permeate H
2
when air rather than 0
2
144
is used as an oxidant in the well-mixed reactor. It was predicted that superficial gas velocities in
excess of 0.3 m/s would be of little benefit.
Dogan et al. (2003) summarized autothermal FBMR modelling results with direct oxygen
addition. Varying the steam-to-carbon ratio showed only a mild effect on hydrogen permeate
yield. The benefits of high temperature operation to produce higher H
2
membrane fluxes were
also highlighted, although the operating temperatures investigated (650 to 850C) are excessive
for the palladium-silver membranes of interest in my work. Rakib and Alhumaizi (2005) also
modelled oxygen addition to an FBMR.
Elnashaie and co-workers have published a number of modelling papers on a circulating fluidized
bed membrane reactor for reforming of natural gas and higher hydrocarbons (e.g. Prasad and
Elnashaie, 2002, Chen and Elnashaie, 2005).
In all of the above models, the kinetics of Xu and Froment (1990) were adapted and combined with
the hydrodynamics of a fluidized bed reactor. All assumed vertical membrane tubes (or U-tubes) and
considered permeate sweep gas to increase the hydrogen flux. In some cases, simulations have
suggested that the use of long vertical tubes in the FBMR would lead to reverse permeation of
hydrogen in the relatively cool freeboard of the reactor (e.g. Abashar et al., 2003). This can be
avoided with planar membrane modules that extract hydrogen over a more limited reactor height
interval.
The above studies also indicated that the kinetics of the SMR process are sufficiently rapid, at least
for temperatures larger than about 550-600C, that chemical equilibrium is very nearly achieved for
FBMR heights and catalysts which are likely to be of practical interest. In addition, the above models
indicate that for Pd membranes with current thicknesses (25 to 75 pm), the membrane flux is the
controlling parameter of the reactor performance. In view of this, it was decided to ignore the SMR
reaction kinetics and simulate the ICFBMR process using equilibrium reactors in a commercial
software environment (HYSYS, version 3.4) in order to create a flexible process design tool. A
commercial simulator permits rapid development of the overall process flow diagram and facilitates
sensitivity analyses and equipment sizing. The only hydrodynamic feature considered in the
simulation is internal circulation of solids, gas and heat.
6.2 Reactor Simulation
The HYSYS model included interna! circulation of catalyst and gas down the annulus and up the
reactor core. SMR equilibrium values from the HYSYS simulation were found to closely match those
predicted by an independent kinetic model. Details on the HYSYS reactor model are presented in
145
Table A6.1.1, Appendix 6.1. The ICFBMR was simulated with a series of Gibbs reactors and
hydrogen separators, as shown schematically in Figure 6.1. The HYSYS flowsheet and algorithm are
presented in Figures A6.1.1 and A6T.2, Appendix 6.1. The reactants modelled wereC H 4 , C
2
H6, CO,
C0
2
, H
2
and H
2
0. Carbon formation is not thermodynamically favoured at these conditions, and was
thus ignored.
I CF BMR
Preheated air)d 1
Core draft box
(10 repeated membrane/
reactor pairs)
Stream key
Gas stream
So lid stream
Heat stream
>
Preheated
C H4 /H2 Q
E. Gas split
D. Gibbs reacto r
(o xidant)
,9.10> <10.1
C10 Gibbs reacto r
(adiabatic)
<6.10> <10.9
B10. Membrane k?i ?
rb.n Gibbs reacto r"
1
L (adiabatic) I
j
-
B.n Membrane |-<^>
C1 . Gibbs reacto r
(adiabatic)
A. Gibbs reacto r
(adiabatic)
14 V-I Rxtr o f f -gas
Heat lo ss
Annul ar
circul ation
(recycle)
Permeate H^)
Figure 6.1: ICFBMR simulation schematic
Preheated steam and methane (1) are mixed with hot circulating solids (2) from the oxidation
zone (D) in a Gibbs reactor (A), representing the area immediately above the main feed
146
distributor. The circulating solids also drag down a portion of the gases (3) from the top of the
reactor (E). The temperature drops as methane and steam react adiabatically in the first Gibbs
reactor (A). Higher catalyst circulation reduces the temperature drop. The temperature at the exit
of the first Gibbs reactor (4) is considered to be the maximum operating temperature of the
membranes.
The gas stream (4) from the Gibbs reactor (A) then flows to the first membrane (Bi) in the draft
tube, where pure, low-pressure hydrogen is removed (8.1). The hydrogen removal shifts the SMR
equilibrium, and the non-permeate gases (6.1) and solids (5) further react in an adiabatic Gibbs
reactor (Ci).
A series of ten membrane / Gibbs reactor pairs then follows, each removing an equal fraction of
the permeate hydrogen. By using a series of reaction / separation steps, the partial pressure
driving force in each membrane set is known, allowing the membrane permeation area to be
calculated. Full chemical equilibrium is assumed for the product stream after each H
2
removal
stage.
Gas (9.10) and solids (10.10) from the last core Gibbs reactor (C.10) leave the core draft box.
These streams react with preheated air (11) in another Gibbs reactor (D). In order to account for
ambient reactor heat losses, a heat stream (12) is rejected by the oxidant reactor (D). The flow of
air (11) is adjusted until the reactor energy balance is satisfied. Note that the simulation reacts
methane with the oxygen, as this minimized the Gibbs free energy. In practise, a portion of the
hydrogen is also likely to be oxidized. In any event, the question of which chemical species is
oxidized is does not practically matter, as the reactor off-gas is combusted in a commercial
system to recover heat for raising steam and preheating feeds, as depicted in Figure 6.10.
Hot catalyst (2) is circulated back to the bottom of the reactor via the annular region of the
reactor. The solids mass flux (G
pcore
, kg/m
2
s) is assumed to be a function of the superficial gas
velocity in the core (Ucore, m/s) and the catalyst particle density (p
p
= 2,100 kg/m
3
), as described
by the correlation developed in Chapter 3 (Figure 3.20) for vertically-slotted panels. As discussed
in Chapter 5, this equation matched the deduced circulation rate in the pilot reactor within 10%:
G
p j a n
=- 0. 000103(^L /
c o r e
)
2
+0. 180(
P p
L /
c o r e
)- 11. 3 (6.1)
In order to set the solids circulation flow (m
pcore
, kg/s), the flow area in the core draft box (A
core
)
is required. This is calculated from the user-inputted superficial core velocity (U
core
) and the
volumetric flow of gas entering the core draft box (stream 4):
A r~* Qcore s~* ff\0\
p,core core p,core j j p,core v^'^v
147
The circulating solids act only as a heat carrier in the simulation. Calcium was selected to
represent the circulating catalyst solids, as AI2O3 was not available in the HYSYS property
database. Calcium is chemically inert in the simulation. As the specific heat of calcium in
HYSYS is slightly lower than that of alumina, the circulation rate expression (equation 6.2) was
multiplied by a specific heat adjustment factor (1.15) to match the heat flow of the circulating
alumina catalyst.
The gas leaving the oxidant Gibbs reactor (13) splits into two compositionally identical streams;
a reactor off-gas stream (14) and a stream recycled back to the bottom of the reactor with the
circulating solids (3). Cold model testing (Chapter 3) suggested that the volumetric downward
flow of gas was approximately equal to the volumetric flow of solids down the annulus. The
volumetric flow of the circulating gas is therefore set by dividing the solids circulation rate
(equation 6.2) by the catalyst bulk density (2,100 kg/m
3
).
The simulation application is somewhat limited as reaction kinetics and hydrodynamics are not
accounted for. In addition, the simulation does not address the following features of the ICFBMR
system:
A very small portion of the methane may flow up the annulus, bypassing the reactor core.
Some heat transfer must occur from the hot annulus zone to the cooler reactor core.
Heat conduction vertically along the membrane panels and supports is neglected.
The simulation effectively assumes plug flow (ten well-mixed stages) of gas and solids up the
reactor core. More than ten stages did not significantly alter the simulation results and added
to computation time. In cold model experiments, a small fraction of the gas and solids were
found to circulate from the oxidation zone to the upper sections of core.
The pressure drop in the reactor is ignored, i.e. the pressure in each of the compartments was
assumed to be the same.
The effective membrane area (A
e
j) for each of the permeation zones can then be calculated from the
simulation output using the hydrogen flux equation for Pd
75
Ag25:
-1
T Q
H
exp(
) ( P H , ? - P H ,
5
)
(6.3)
k
H
R T
where T is the membrane thickness (base case 50E-6 m).
Q
H
is the H
2
permeation per stage (base case 30 Nm /h/10 stages = 0.037 mol/s).
k
H
= 3.43E-7 mol/m s Pa
05
(see Chapter 2)
148
E
p
= 9,180 J/mol (see Chapter2)
T is the permeation temperature (K), assumed to be equal to the temperature of the
reactor gas entering each membrane separation stage.
P H I , is the hydrogen partial pressure in the reactor (Pa). For each permeation zone,
Put, is assumed to be the average of that zone's inlet and outlet equilibrium partial
pressures.
P
H
i is the hydrogen partial pressure in the permeate stream (Pa). The base case is
atmospheric pressure (101 kPa), without any sweep gas.
6.2.1 S i mul ati on Base Case
The main reactor simulation variables and their base values are listed in Table 6.1. A summary of the
main process streams for the base case is presented in Table 6.2. Refer to Figure 6.1 for
nomenclature. Full stream output data for the base case simulation are presented in Table A6.1.2,
Appendix 6.1.
As indicated in Table 6.1, the target value for the permeate hydrogen to methane molar ratio was2/2.
Higher hydrogen recovery is achievable if more membrane area is installed. However, when the
overall system is considered, a hydrogen recovery between2.5 to2.7 is likely to be an optimal, as the
reactor off-gas containing methane, CO and unrecovered H2 is combusted to preheat the reactor
feeds. If a higher hydrogen recovery were used, additional natural gas would be required to
supplement the burner duty. This process configuration is presented in Section 6.3.
The base case simulation output appears reasonable. The oxidation zone was calculated to be 18C
hotter than the inlet temperature of the reactor core (600C). The oxidation temperature is a function
of the solids circulation rate, the preheat temperature of the reactor feeds and the specified maximum
membrane temperature. The flow of oxidation air was adjusted to satisfy the reactor energy balance,
resulting in an 02:CH4 molar ratio of 0.39. Approximately 10%of the gases in the upper reactor were
estimated to recycle to the reactor core with the circulating solids. Due to hydrogen removal,
partially countered by the increase in molar flow due to reaction, the number of moles of gas leaving
the reactor core (excluding permeate H
2
) is approximately two-thirds of the gas entering the core.
149
Table 6.1: ICFBMR base case simulation
Variable description Base case Notes
Reactor pressure 2,500 kPa Max 1,500 kPa in ICFBMR pilot plant
<D
Total permeate H
2
flow 30 Nm
J
/h
Lower side for distributed H
2
market
J O
.2
Steam-to-carbon molar ratio of feed 3.0 Typical industrial value
a
> Permeate FbjCFL, ratio 2.5 Reasonable objective
c
<D
T 3
C
Superficial core velocity (U
core
) 0.25 m/s Based on cold model tests
u
D .
CU
TD
Max membrane operating temperature 600C Temperature of stream 4 in Figure 6.1
C
Feed preheat temperature 600C Assures energy integration
Reactor heat losses 2kW -10%of endothermic reaction heat
i
r
i
a
b
l
e
s
C H 4 flow 12Nm7h Set by H
2
flow and H
2
recovery
i
r
i
a
b
l
e
s
Steam flow
36NmVh Set by CFL, flow and H
2
0:CFL| ratio
TO
>
3
GvCFL, molar ratio 0.39 Adjusted by reactor heat balance
1)
-a
c
Solids circulation 1,356 kg/h Set by correlation with U
cor
e (Eq. 6.2)
a,
Q
Oxidation zone temperature 618C
Adjusted to match maximum
membrane operating temperature
Membrane thickness (r) 50E-6 m Readily commercially available
<8
c
Permeate sweep gas
None
Reduces connections and ensures
product impurities
M
e
m
l
Permeate pressure 101 kPa No vacuum equipment required
M
e
m
l
Membrane efficiency 100% Area predicted by Eq. 6.3
150
Table 6.2: Stream summary for 30 Nm Th reactor base case simulation
(Note: Stream numbers refer to Figure 6.1)
Stream 1 2 3 4 5 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 8.2
Mass Flo w [kg/h] 37.55 1558.98 5.33 42.88 1559 42.61 42.34 42.07 41.80 41.53 41.26 40.99 40.72 40.45 40.18 0.27
Vo lumetric f lo w [m3/h] 6.18 1.14 0.65 7.61 1.14 7.21 6.93 6.65 6.37 6.10 5.83 5.57 5.32 5.07 4.82 9.66
Mo lar Flo w [kmol/h] 2.14 38.90 0.22 2.62 38. 90 2.49 2.40 2.31 2.22 2.14 2.05 1.97 1.89 1.80 1.72 0.13
Temperature [C] 600 618 618 600 600 600 597 594 592 588 585 582 579 575 572 603
Pressure [kPa] 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 101
Heat Flo w [kJ/h] -3.79E+05 7.63E+06 -3.27E+04 -3.86E+05 7.61E+06 -3.88E+05 -3.87E+05 -3.85E+05 -3.83E+05 -3.81 E+05 -3.79E+05 -3.77E+05 -3.75E+05 -3.72E+05 -3.70E+05 2.27E+03
Mo le f ractio n -CH4 0.25 0 0.0131 0.1551 0 0.1634 0.1607 0.1572 0.1530 0.1480 0.1421 0.1352 0.1274 0.1187 0.1086 0
Mo le f ractio n - CO 0 0 0.0154 0.0084 0 0.0088 0.0096 0.0103 0.0110 0.0116 0.0122 0.0128 0.0133 0.0137 0.0141 0
Mo le f ractio n - C02 0 0 0.1778 0.0578 0 0.0609 0.0718 0.0839 0.0973 0.1122 0.1288 0.1471 0.1672 0.1895 0.2140 0
Mo le f ractio n -H2 0 0.75 0 0.4095 0.5532 0 0.5830 0.5877 0.5913 0.5940 0.5959 0.5968 0.5961 0.5947 0.5925 0.5885 0
Mo le f ractio n - N2 0 0 0.3040 0.0252 0 0.0266 0.0276 0.0286 0.0298 0.0310 0.0323 0.0336 0:0351 0.0367 0.0384 0
Mo le f ractio n - 02 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Mo le f ractio n - H2 0 0 0.0802 0.2003 0 0.1572 0.1428 0.1287 0.1150 0.1013 0.0878 0.0751 0.0623 0.0489 0.0365 1.000
Mo le f ractio n - Ca 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0
Sream 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 10.1 11 12 13 14 15
Mass flo w [kg/h] 42.61 42.34 42. 07 41. 80 41. 53 41.26 40.99 40.72 40.45 40.18 1559 28.84 - 69.02 63. 69 2.70
Vo lumetric flo w [m3/h] 7.32 7.04 6.76 6.49 6.22 5.96 5.70 5.45 5.20 4.96 1.14 2.92 - 8.35 7.71 95.5
Mo lar Flo w [kmol/h] 2.53 2.44 2.36 2.27 2.19 2.10 2.02 1.94 1.86 1.78 38.90 1.00 - 2.81 2.60 1.34
Temperature [C] 597 594 592 588 585 582 579 575 572 569 597 600 618 618 593
Pressure [kPa] 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 - 2500 2500 101
Heat Flo w [kJ/h] -3.85E+05 -3.83E+05 -3.81 E+05 -3.79E+05 -3.77E+05 -3.75E+05 -3.73E+05 -3.70E+05 -3.68E+05 -3.65E+05 7.61E+06 1.76E+04 7.20E+03 -4.23E+05 -3.90E+05 2.23E+04
Mo le f ractio n -CH4 0.1522 0.1486 0.1443 0.1392 0.1333 0.1266 0.1190 0.1105 0.1008 0.0902 0 0 - 0.0131 0.0131 0
Mo le f ractio n - CO 0.0091 0.0097 0.0103 0.0109 0.0115 0.0120 0.0124 0.0128 0.0131 0.0133 0 0 - 0.0154 0.0154 0
Mo le f ractio n - C02 0.0680 0.0793 0.0918 0.1056 0.1209 0.1378 0.1562 0.1763 0.1987 0.2230 0 0 - 0.1778 0.1778 0
Mo le f ractio n -H20 0.5566 0.5589 0.5603 0.5606 0.5600 0.5582 0.5554 0.5515 0.5463 0.5400 0 0 - 0.4095 0.4095 0
Mo le f ractio n - N2 0.0261 0.0271 0.0281 0.0291 0.0303 0.0315 0.0328 0.0341 0.0356 0.0372 0 0.79 - 0.3040 0.3040 0
Mo le f ractio n - 02 0 0 0 0 0 0 0 0 0 0 0 0.21 - 0 0 0
Mo le f ractio n - H2 0.1881 0.1764 0.1652 0.1545 0.1441 0.1340 0.1243 0.1148 0.1055 0.0963 0 0 - 0.0802 0.0802 1
Mo le f ractio n - Ca 0 0 0 0 0 0 0 0 0 0 1 0 - 0 0 0
Figure 6.2 presents the temperatures and average hydrogen partial pressures for the ten membrane
permeation stages for the base case (stage 1 is at the bottom, 10 at the top). A significant temperature
drop (~30C) is predicted over the reactor core. Another item of note is the reduction in the hydrogen
partial pressure as gases flow up the reactor core, corresponding to a reduced permeation driving
force. The reactor-side H
2
partial pressure in the final permeation stage is -250 kPa, still well above
the base case permeate-side pressure (101 kPa).
600 600
200
1 8 10 2 3 4 5 6 7
Hydrogen removal stage
Figure 6.2: Permeation stage temperature and reactor hydrogen partial pressure (base case)
Each membrane stage in the simulation is assumed to permeate an equal flow of hydrogen. However,
as the temperature and hydrogen partial pressure are reduced as the gases pass upward through the
reactor core, the permeation area required for each stage increases (see "adiabatic"curve in Figure
6.3). The permeation area in the last stage is approximately twice that required for the first H
2
stage,
indicating that membrane panels at the bottom of the reactor would produce more H
2
than panels of
equal area located higher in the reactor core. The total permeation area (for the assumed 50 um thick
membrane) is the sum of the areas of all permeation stages, calculated to be 2.34 m
2
. As the
calculated permeation area (equation 6.3) is proportional to the membrane thickness, 25 urn thick
membranes would halve the required membrane.
If the internal solids circulation were very high, the reactor core would approach isothermal
operation. The effect of an isothermal core (600C) on membrane area is also presented in Figure 6.3
("isothermal"curve). The total membrane area is calculated to be 2.01 m
2
for the isothermal case,
14%less than calculated if the core operated adiabatically.
152
0.4
0 -I , , , 1 , 1 1 1 1
1 2 3 4 5 6 7 8 9 10
Hydrogen removal stage
Figure 6.3: Calculated permeation stage area (base case, 50 um Pd
75
Ag25 membrane)
6.2.2 Effect of Reac tor Vari ab l es
The influence of the major process variables on the ICFBMR design was investigated by parametric
studies using the HYSYS simulation. Perhaps the most important ICFBMR reactor design
characteristic is the required membrane area. As the ICFBMR reactor geometry is governed by the
membrane layout, the total reactor volume can be estimated based on the calculated membrane area.
One of the disadvantages of the ICFBMR design is that it tends to have a low overall space velocity
relative to fixed bed configurations. It is therefore important to reduce the membrane area in order to
produce a compact reactor design. In addition, the palladium membranes represent a significant
system cost.
Reactor pressure: Figure 6.4 demonstrates the strong effect of reactor operating pressure on the
predicted membrane area. Increasing reactor pressure above 2,500 kPa decreases the area only
marginally. The calculated membrane area is normalized to the base case (2.34 m
2
). The solids
circulation rate was assumed to be only a function of the superficial core velocity (equation 6.1,
above). If the core superficial velocity is held constant, increasing the reactor pressure reduces
the solids circulation rate as it decreases the flow area in the reactor core (A
core
). Decreasing the
solids circulation increases the temperature drop in the reactor core, increasing the membrane
area. The data in Figure 6.4 account for this effect.
Steam-to-carbon ratio: Also shown on Figure 6.4 is the effect of the steam-to-carbon ratio on the
normalized membrane area. Given the weak effect for the limited range considered, other issues
are likely to govern the preferred steam-to-carbon ratio, such as the potential for carbon
formation on the catalyst at low molar ratios.
153
2.5
1,000 1,500 2,000 2,500 3,000
Reactor pressure (kPa)
Figure 6.4: Effect of reactor pressure and steam-to-carbon ratio on normalized base case membrane
area (50 um Pd
75
Ag
25
membranes)
Hydrogen recovery: Figure 6.5 presents the influence of hydrogen recovery (moles of permeate
H
2
per mole of CFL, fed to the reactor) on the normalized membrane area at reactor pressures of
1,500 and 2,500 kPa. As expected, the membrane area requirement increases with increasing
hydrogen recovery. Hydrogen recoveries beyond a H
2
:CHt molar ratio of 3.0 become
progressively more difficult, as the hydrogen partial pressure in the reactor becomes very low,
and reaction kinetics may become limiting. Also shown in Figure 6.5 is the required 0
2
to CFL,
molar ratio as a function of hydrogen recovery. As more hydrogen is removed from the reactor,
the reaction duty increases, as more oxidation air is required to generate the heat needed for
autothermal operation.
H2 product:CH4 feed molar ratio (-)
Figure 6.5: Effect of hydrogen recovery on normalized base case membrane area
154
Membrane temperature: The base case assumes a maximum operating temperature of 600C. The
ICFBMR pilot reactor membranes operated at temperatures up to 650C. Increasing the
membrane operating temperature strongly decreases the membrane area as it increases the
specific membrane flux (see equation 6.3) and, more importantly, favourably shifts the SMR
equilibrium. However, operation at temperatures below 600C, and perhaps as low as 550C, is
likely needed for successful long-term operation of palladium-based membranes. Figure 6.6
clearly illustrates the incentive for the development of high-temperature membranes.
2.0
0.5 I , , 1 1
550 575 600 625 650
Maximum membrane operating temperature (C)
Figure 6.6: Effect of membrane operating temperature on normalized base case membrane area
Feed preheat temperature: The base case assumes that the feed streams (steam, methane and air)
enter the reactor at 600C. Figure 6.7 demonstrates that the normalized membrane area is
relatively insensitive to the feed preheat temperature, despite the significant change in the
required flow of oxidation air. This highlights how the ICFBMR facilitates circulation of heat
within the reactor, but not nitrogen from the oxidation air, which would otherwise reduce the H
2
flux through the membrane.
155
1.25
0.50
0.75
400
700 500 600
Feed preheat temperature (C)
Figure 6. 7: Effect of feed preheat temperature on normalized membrane area
Solids circulation rate: Increasing the solids circulation rate decreases the temperature drop in the
reactor core (Figure 6. 8). An isothermal core will result in higher fluxes and improved reactor
equilibrium in the upper reactor core. If solids circulation is lower than predicted in the
simulation, there is a penalty on the predicted membrane area. Increasing solids circulation
beyond the base case has only a modest effect on membrane area.
1.25
CU
k-
ro
0)
c
CO
I.
n
E
cu
E
TJ
CU
N
~m
E
i_
o
z
1.00
0.75
--Area
-o-Temperature
0 1 2 3 4
Normalized solids circulation (-)
Figure 6. 8: Effect of normalized solids circulation rate on normalized base case membrane area
Increased solids circulation transports more gas from the top of the reactor, diluting the hydrogen
in the reactor core, thus modulating the benefits of a more isothermal core. As noted above, it was
assumed here that the gas circulation is volumetrically equal to that of the catalyst circulation.
156
Hence, as solids circulation increases, more nitrogen is circulated to the core, thereby reducing
the hydrogen partial pressure. At very high solids circulation, the benefits of an increasingly
isothermal reactor core are slightly outweighed by the nitrogen dilution effect, and the area curve
turns slightly upward.
P ermeate pressure: Reducing the permeate H
2
partial pressure increases the driving force for
permeation, thus reducing the required membrane area. This may be achieved in membrane
reactors by utilizing permeate-side sweep gas. If a high-purity H
2
product were desired, the only
sweep gas that may be practical would be steam. However, the heat duty to generate sweep steam
reduces the overall thermal efficiency of the process, produces a wet hydrogen product, and
introduces impurities unless the water used to make the steam were to be subjected to rigorous
purification. A more practical method of enhancing the hydrogen flux may be to expose the
permeate stream to vacuum. However, there is a risk that vacuum operation could cause ingress
of air into the permeate H
2
, adding impurities to the hydrogen product and creating safety and
fiammabilify issues. Vacuum operation would also add to hydrogen compression costs. However,
as shown in Figure 6.9, there can be a significant reduction in membrane area with vacuum
operation.
X 2. 5 -i
RS
CO U. O "
E
z 0.0 -! ! 1 ' 1
0 50 100 150 200
Permeate H2 partial pressure (kPa)
Figure 6.9: Effect of permeate H
2
partial pressure on normalized base case membrane area
6.3 Design of a 30 Nm
3
/h ICFBMR
To assess the costs and performance of a commercial ICFBMR system, a design for a 30 Nm
3
/h
hydrogen production unit was developed with the HYSYS process simulator. This capacity is five
times larger than the nominal design rate of the ICFBMR pilot reactor, and would be sufficient to
support a fleet of about 150 fuel cell cars. The design assumes autothermal SMR operation using
157
direct air addition, with no external heat transfer to the reactor. At this capacity, the endothennic
SMR duty is approximately 20 kW, a reasonably large value for indirect transfer in a conventional
SMR design, but one that could be readily handled in an autothermal ICFBMR design.
6.3.1 Design Basis
The main feeds are natural gas, city water and atmospheric air (Table A6.1.3, Appendix 6.1). Based
on recent MRT operating experience (Li, 2005a), 25 um thick Pd
75
Ag25 membranes are chosen, but
are derated by 50%to account for membrane and reactor inefficiencies and thus modeled as 50 um
thick. The design assumes most of the reactor base case conditions presented previously.
Autothermal operation: The reactor is assumed to operate adiabatically through direct air
addition. Electrically powered heaters are installed for reactor start-up, but are not used for
normal operation. Preheating of steam and feed is accomplished through heat exchange with
combusted reactor off-gas.
Reactor conditions:
o 2,500kPa reactor pressure.
o 3.0 steam-to-carbon molar feed ratio.
o 2/4 moles of hydrogen product per mole of feed methane.
o 2 kW reactor heat loss.
Membranes:
o Maximum 600C operating temperature.
o 25 urn thick, palladium silver (25%) membranes, derated by 50%.
o Pure hydrogen product (i.e. no sweep gas).
o Maximum operating temperature of membranes of 600C.
o Permeate pressure is 101 kPa.
Hydrogen product:
o The hydrogen permeate stream is compressed to 3,000 kPa.
o Hydrogen storage and dispensing is outside the scope of the process design.
Reactor geometry and hydrodynamics:
o Superficial gas velocity within the range of 0.1 to 0.3 m/s, with the final velocity to be
determined by layout considerations,
o Membranes arranged with vertical communication slots between adjacent flow channels.
158
Burner. The non-permeate reactor off-gas has fuel value from residual C H 4 , CO and H
2
. It is
combusted to generate the high-temperature flue gas needed to raise steam and preheat the reactor
feed. The burner duty can be supplemented by fresh natural gas if necessary.
6.3.2 Process S i mul ati on
Several process options, mainly focused around heat integration, were considered in developing the
flowsheet. The process flow diagram and associated stream table are shown in Figure 6.10 and Table
6.3 respectively. Figure A6.1.4 in Appendix 6.1 presents the process flow schematic output from the
HYSYS simulation. The major unit operations included in the 30 NnvVh PFD include:
Water treatment: City water is treated in a mixed ion exchange bed to remove trace hardness and
organic compounds. Treated city water is combined with water recovered from the reactor off-
gas, then pumped to the process.
Natural gas treatment: Natural gas is desulfurized in two parallel beds of ZnO adsorbent.
Gas compression: Natural gas and oxidation are compressed to 100 kPa above the reactor
pressure. An adiabatic efficiency of 75%is assumed for the compressors. Inter-stage compressor
cooling is assumed to reject heat to ambient air.
Burner: Non-permeate reactor off-gas is combusted in a forced draft burner. Excess air is
adjusted to achieve the desired burner operating temperature. Increasing the burner temperatures
(i.e. minimizing excess air) results in higher overall system efficiencies. However, a maximum
burner operating temperature of 1,000C is imposed to allow standard materials of construction
to be used. A heat loss of 2 kW from the burner to the environment is assumed to account for
non-reactor heat losses. The bulk of the burner duty is provided by the reactor off-gas. A small
amount of natural gas is also combusted to represent the burner pilot flame.
Heat exchange: Steam is raised and the reactor feeds preheated through heat exchange with
reactor off-gas and burner gas.
ICFBMR: Preheated natural gas and steam react to form hydrogen, most of which is extracted by
the membranes to produce a high-purity H
2
stream. Sufficient air is added to allow the reactor to
operate adiabatically (with a 2 kW ambient heat loss allowance). After the non-permeate reactor
off-gas (ROG) leaves the reactor, it is cooled and condensed. Condensate is recycled back to the
feed water tank. The residual heating value in the cooled ROG is recovered in the burner.
H2 compression: The hydrogen permeate is compressed in a multistage compressor.
159
Table 6.3: Stream table for 30 Nm
3
/h flowsheet
Stream 1 2 3 4 5 7 8 9 10 11 13 14 15 16 20 21
Mass Flow [kg/h] 8.69 . 8.59 8.59 8.59 11.12 28.93 28.93 28.93 37.52 37.52 2.69 2.69 2.69 2.69 63.78 63.78
Actual Volume Flow [m3/h] 10.78 10.66 0.73 1.44 0.011 0.030 0.14 0.94 2.23 6.18 95.90 62.88 34.36 1.21 7.73 6.53
Molar Flow [kgmole/h] 0.541 0.535 0.535 0.535 0.617 1.606 1.606 1.606 2.142 2.142 1.332 1.332 1.332 1.332 2.603 2.603
Temperature [C] 15 15 160 564 15 68 226 226 203 600 601 300 40 50 618 482
Pressure [kPa] 120 120 2600 2600 300 2600 2600 2600 2600 2500 101 101 101 3000 2500 2500
Vapour Fraction 1 1 1 1 0 0 0.05 0.40 0.72 1 1 1 1 1 1 1
Molecular Weight 16.04 16.04 16.04 16.04 18.02 18.02 18.02 18.02 17.52 17.52 2.02 2.02 2.02 2.02 24.50 24.50
Mass Density [kg/m3] 0.81 0.81 11.71 5.96 1015 975 200 30.90 16.80 6.07 0.03 0.04 0.08 2.23 8.26 9.78
Viscosity [cP] 1.09E-02 1.09E-02 1.56E-02 2.48E-02 1.14E+00 4.13E-01 - - - 2.66E-02 1.97E-02 1.52E-02 9.16E-03 9.48E-03 3.27E-02 2.91E-02
Thermal ConductivityJW/m-K] 3.23E-02 3.23E-02 5.66E-02 1.33E-01 5.95E-01 6.61E-01 - - - 9.24E-02 3.79E-01 2.84E-01 1.82E-01 1.88E-01 8.03E-02 6.87E-02
Mass Heat Capacity [kJ/kg-C] 2.23 2.23 2.71 4.08 4.05 4.05 4.83 3.87 3.02 2.70 14.73 14.60 14.12 14.26 1.62 1.56
Heat Flow [kJ/h] -4.08E+04 -4.03E+04 -3.74E+04 -2.56E+04 -1.76E+05 -4.52E+05 -4.30E+05 -4.11E+05 -4.36E+05 -3.78E+05 2.25E+04 1.07E+04 5.67E+02 9.54E+02 -3.90E+05 -4.04E+05
Comp Mole Frac (Methane) 1 1 1 1 0 0 0 0 0.25 0.25 0 0 0 0 0.013 0.013
Comp Mole Frac (CO) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.015 0.015
Comp Mole Frac (C02) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.177 0.177
Comp Mole Frac (H20) 0 0 0 0 1 1 1 1 0.75 0.75 0 0 0 0 0.409 0.409
Comp Mole Frac (Nitrogen) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.304 0.304
Comp Mole Frac (Oxygen) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Comp Mole Frac (Hydrogen) 0 0 0 0 0 0 0 0 0 0 1 1 1 1 0.081 0.081
Stream 22 23 24 26 27 30 31 32 35. 36 37 38 39 40 41
Mass Flow [kg/h] 63.78 63.78 63.78 45.94 17.84 28.95 28.95 28.95 0.10 43.28 43.28 43.28 89.31 89.31 89.31
Actual Volume Flow [m3/h] 4.43 3.70 1.99 40.84 0.019 23.71 1.40 2.82 0.12 35.44 34.90 56.21 302.05 173.99 127.44
Molar Flow [kgmole/h] 2.603 2.603 2.603 1.614 0.990 1.003 1.003 1.003 0.006 1.500 1.500 1.500 2.995 2.995 2.995
Temperature [C] 250 177 100 92 100 15 160 600 15 15 21 200 952 432 245
Pressure [kPa] 2500 2500 2500 120 2500 101.3 2600 2600 120 101.325 105 105 101 101 101.3
Vapour Fraction 1 0.99 0.62 1 0 1 1 1 1 1 1 1 1 1 1
Molecular Weight 24.50 24.50 24.50 28.47 18.03 28.85 28.85 28.85 16.04 28.85 28.85 28.85 29.82 29.82 29.82
Mass Density [kg/m3] 14.41 17.22 32.06 1:12 949 1.22 20.73 10.25 0.81 1.22 1.24 0.77 0.30 0.51 0.70
Viscosity [cP] 2.13E-02 1.96E-02 2.79E-01 1.83E-02 2.49E-02 4.29E-02 1.09E-02 1.83E-02 1.86E-02 2.63E-02 4.99E-02 3.20E-02 2.57E-02
Thermal Conductivity [W/m-K] 4.81 E-02
- 3.72E-02 6.81E-01 2.52E-02 3.55E-02 6.06E-02 3.23E-02 2.52E-02 2.56E-02 3.71 E-02 8.01 E-02 5.04E-02 3.82E-02
Mass Heat Capacity [kJ/kg-C] 1.49 1.50 2.01 1.15 4.10 1.01 1.05 1.13 2.23 1.01 1.01 1.03 1.32 1.17 1.11
Heat Flow [kJ/h] -4.27E+05 -4.35E+05 -4.80E+05 -2.03E+05 -2.76E+05 -3.01E+02 3.89E+03 1.76E+04 -4.52E+02 -4.50E+02 -1.92E+02 7.71 E+03 -2.03E+05 -2.61 E+05 -2.80E+05
Comp Mole Frac (Methane) 0.013 0.013 0.013 0.021 0.000 0 0 0 1 0 0 0 0 0 0
Comp Mole Frac (CO) 0.015 0.015 0.015 0.025 0.000 0 0 0 0 0 0 0 0 0 0
Comp Mole Frac (C02) 0.177 0.177 0.177 0.285 0.001 0 0 0 0 0 0 0 0.181 0.181 0.181
Comp Mole Frac (H20) 0.409 0.409 0.409 0.048 0.999 0 0 0 0 0 0 0 0.123 0.123 0.123
Comp Mole Frac (Nitrogen) 0.304 0.304 0.304 0.491 0.000 0.79 0.79 0.79 0 0.79 0.79 0.79 0.660 0.660 0.660
Comp Mole Frac (Oxygen) 0 0 0 0 0 0.21 0.21 0.21 0 0.21 0.21 0.21 0.036 0.036 0.036
Comp Mole Frac (Hydrogen) 0.081 0.081 0.081 0.130 0.000 0 0 0 0 0 0 0 0 0 0
Heat stream H1 H2 H3 H4 H5 H6 H7
Heat Flow [kJ/h] 7,200 7,200 21,388 4,524 39,405 10,104 45,142
A pinch analysis was performed to look at possible heat recovery schemes (see Figure A6.1.3 and
Table A6.1.4, Appendix 6.1). The pinch temperature is 225C, the feed steam boiling point. The
reactor pressure has a significant impact on the pinch analysis, as it sets the boiling temperature of the
feed steam. The burner gases are vented to atmosphere at ~250C, ensuring a positive temperature
driving force to raise steam. Table 6.4 summarizes the PFD feed and utility consumptions. The molar
ratio of permeate (pure) hydrogen to total natural gas consumed is 2.48.
Table 6.4: PFD stream summary for 30 Nm
3
/h design
Description PFD value Notes
Natural gas 12.1 Nm7h 0.1 Nm
J
/h to burner, balance to reformer
T3
<U
<U
Air 56 Nm
J
/h Atmospheric air, 60%to burner, balance to reformer
lu
Water 11 kg/h Water recovery from ROG reduces consumption
<*>
Cooling water ~2 m
J
/h Air coolers could eliminate use of cooling water
'-*-
Nitrogen 0 Nm7h Used to purge system for start-up and shutdown
5
Electricity 21 kW Compressors
If electrical power is ignored, the energy efficiency of conversion of the methane to hydrogen is 80%,
based on the higher heating values of hydrogen and methane. The overall energy efficiency O7) is
calculated to be 69%, based on the electrical power consumed and higher heating values of methane
and hydrogen.
HHV
H2
(134kmol I h)(2S6MJ I kmol) _
Q 6 9
.
V
~ HHV
CH4
+ power ~ (0.536kmol / h)(S9lMJ / kmol) + (Q.021MJ/s)(3600s/h) ~
Table A6.1.5 (Appendix 6.1) summarizes the process losses. Waste heat from the compressors and
condensation of the reactor off-gas accounts for the bulk of the thermal inefficiency. It is difficult to
recover energy from these low-grade sources within the process, though most of the rejected heat
could be captured for domestic hot water and space heating.
6. 3. 3 R e a c t o r L a y o u t
Experience gained in design and fabrication of the ICFBMR pilot reactor (Chapter 4) showed that the
layout of the reactor internals poses a number of mechanical challenges. One of the biggest issues
was the numerous membrane tubes and instruments that had to be neatly fixed within the reactor and
sealed at the reactor shell. Minimizing the number of vessel connections is clearly important.
162
Another consideration is the size of commercially available palladium foil. It is difficult for suppliers
to cold-roll wide strips of very thin palladium. Foils of area 6"x 12"(0.15 x 0.30 m) are available
down to 25 urn thickness. Foils of 3"x 12" (0.076 x 0.30 m) are also now available down to 15 urn.
In order to minimize wastage of palladium, membrane panels based on a foil widthof 3" (0.076 m) or
6"(0.15 m) are likely to be preferred.
The base case simulation assumes a superficial core velocity of 0.25 m/s, from which the core flow
area is then calculated to be 0.0068 m
2
. Figure 6.11 presents one possible membrane layout, based on
a nearly-square core draft box and five staggered membrane panels of the same dimensions as in the
ICFBMR pilot reactor (83 mm wide, 6 mm thick). In order to reduce the core box dimensions, the
space between the membrane panels was set at 13 mm, slightly smaller than the panel spacing in the
pilot reactor and cold model (16 mm). The core box can fit within a 6"(0.15 m) reactor shell. The
area available in the core for flow of this layout is 0.0076 m
2
, corresponding to a superficial core
velocity of 0.22 m/s.
6"shell (0.15 m)-^
v
All dimensions in mm
Membrane
panel
Core box
Figure 6.11: Plan view of option 1 layout - 30 Nm
3
/h reactor (U
core
= 0.22 m/s)
64 membrane panels would be required to match the membrane area calculated for the base case
(2.34 m
2
) for the Option 1 layout. This would require 13 membrane panel stacks, making the core box
almost 4 m tall, an impractical dimension. Thinner membranes would reduce the membrane area,
reducing the reactor height. However, basing a design on 50 urn (or 25 um membranes working at
163
50%efficiency) is currently more realistic. Alternatively, the superficial gas velocity in the core
could be reduced from the original specification of 0.25 m/s. As the solids circulation flux varies
approximately linearly with superficial velocity, decreasing the core velocity will not likely penalize
the design significantly.
An alternative reactor layout is presented in Figure 6.12. In this layout, 6%"x 12"(0.16 x 0.30 m)
membrane panels are installed in a staggered pattern, 13 mm apart within the central zone of the
reactor. The area open to flow in the core in this layout is 0.014 m
2
, corresponding to a core velocity
of 0.12 m/s. The circulating solids travel in two opposing segments rather than in an annular region.
30 membrane panels in six stacks provide the membrane area. The membrane area can be
accommodated in an 8"(0.20 m) diameter, ~2.6 m tall reactor (Figure 6.13). This layout has a lower
proportion of the area for return of solids than in the pilot plant reactor, and additional cold model
testing would be required to verify that sufficient solids circulation could be achieved with this
layout. Figure 6.13 shows the permeate H
2
connecting through the top flange, but the side flange
configuration presented in Figure 4.21 (Chapter 4) could also be used.
164
Off-gas
CH4 /H2 0
Wind
box
i L
Filter
Disengagement zo ne
Settled catalyst bed
Oxidant distributo r
Co re bo x
Membrane
panels (30)
8" (0.31 m) shell
Figure 6.13: Elevation drawing for Option 2-30 NmVh reactor (U
core
= 0.12 m/s)
As the reactor is not heated externally, conventional stainless steel can be used for the reactor shell.
In order to accelerate heat-up of the reactor, several small tubular heaters could be installed in both
solids return zones.
165
6. 3. 4 Ec onomi c s
A simplified economic analysis was performed to estimate costs to build and operate the 30 NmVh
ICFBMR unit. It should be noted that the values presented here are not optimized and are for a one-
off system. Costs to produce multiple units of a production-type design would be significantly less
than values presented, as engineering, capital and fabrication costs could be reduced and amortized
over many units. However, the economic analysis gives a starting point for comparison of the
ICFBMR technology against other emerging small-scale H
2
technologies. Unless otherwise noted, all
costs are in 2006 Canadian dollars.
6.3.4.1 Equipment Costs
A simplified piping and instrumentation drawing (PID) is presented in Figures A6.2.1 and A6.2.2 of
Appendix 6.2. An equipment list, which includes nominal sizing, materials of construction and
estimated capital costs, is presented in Table A6.2.1, Appendix 6.2.
In Chapter 2, the cost to produce the 50 urn thick Pd7sAg
25
membranes used in the ICFBMR pilot
plant was estimated at $40,700/m
2
. Given the larger number of membranes (30), a larger palladium
area and thinner Pd material (25 um) compared to the pilot ICFBMR, the capital cost estimate for the
30 NmVh design assumes a fabricated membrane cost of $10,000/m
2
CAD. Note that the palladium
value in the 25 um membranes is approximately $2,000/m
2
at the average Pd price for the last five
years ($279US/oz, average 2002-2007). This implies that the fabricated membrane cost should be
relatively insensitive to small variations in the spot palladium market.
Bare equipment cost is estimated at $220,000CAD, the breakdown of which is presented in Figure
6.14. Membranes represent -10%of the estimated bare equipment cost. The three gas compressors
are the largest component of the equipment capital. By applying a Lang factor of 3.5 to the bare
equipment cost, the total capital cost to supply the first 30 NmVh ICFBMR unit is estimated to be
$770,000. Use of a simple Lang factor is not appropriate for estimating costs of multiple production
units, as it overestimates engineering and installation costs, but can be justified for the first ICFBMR
skid.
166
Burner
Miscel l aneous
Reactor
(excluding
membranes)
Membranes
Figure 6.14: Estimated 30Nm /h bare equipment cost components (values listed in Table A6.2.1)
6.3.4.2 Operating Costs
The list of assumptions (Table A6.2.2, Appendix 6.2) of the economic analysis of the 30 NmVh base
case includes:
8,000 hours of operation/year, at an average production rate of 85%.
The membranes are replaced annually. No credit is given for recycling palladium, as this
represents only a portion (likely less than 10%) of the membrane replacement costs.
Catalyst and desulfurizer adsorbent are replaced annually.
Inflation rate of 2% applied to consumables and utilities.
Annual maintenance costs are estimated at 5%of bare equipment cost, plus an additional $5,000
for each membrane changeover.
Other miscellaneous expenses, such as insurance and annual taxes, are assumed to be 5%of bare
equipment cost.
Based on the above assumptions, the variable operating costs are estimated to be $5.00/kg of Fb, the
breakdown of which is presented in Figure 6.15 (see data in Table A6.2.3, Appendix 6.2). When gas
and electricity are excluded, the variable operating costs are estimated to be $2.88/kg H
2
. Membrane
replacement represents the largest operating cost component, slightly larger than the cost of natural
gas. Clearly there is a significant economic incentive to reduce operating costs by extending
membrane service life and reducing fabricated membrane costs.
167
Natural gas
(base case, values listed in Table A6.2.3)
6.3.4.3 Cost Recovery
A cash flow analysis was performed to calculate the hydrogen selling price required to recover the
capital and operating costs. Assumptions included:
Cost of capital 10%.
Capital depreciated (double-declining) over the 10-year service life.
Margin tax rate of 38%.
No scrap value for equipment.
The cash flow analysis is presented in Tables A6.2.3 and A6.2.4, Appendix 6.2. Capital recovery was
estimated at $7.00/kg H
2
, which when combined with operating costs, gave a selling price of $ 12.7/kg
H
2
. Given the one-off nature of this design, it is not surprising that the break-even H
2
price is very
high (see Figure 1.2 in Chapter 1 for current H
2
delivery costs). Government subsidies or other
financial incentives would likely be required to make the first ICFBMR unit economically viable.
An alternate economic analysis was performed to compare the ICFBMR technology with
conventional small-scale reformers on a similar footing. Costs for the 30NmVh ICFBMR unit where
compared to estimates for a 222 NmVh small-scale conventional SMR filling station using the same
cost scaling parameters from a recent hydrogen study (Table E-35 in "The Hydrogen Economy",
National Academy of Engineering, 2004). The basis and output from this analysis are presented in
Appendix 6.3.
Using the NAE methodology, the cost of hydrogen production, which included capital recovery, was
calculated to be $4.12 and $6.73/kg H
2
for small-scale conventional SMR and the 30NmVh ICFBMR
168
systems respectively. This estimated cost for the ICFBMR system is approximately half that
estimated using the NPV analysis presented above, with the reduction mostly a result of aggressive
capital cost factors appropriate for a multiple production unit.
A portion of the estimated price difference between the conventional SMR (222 Nm
3
/h) and
ICFBMR (30 Nm
3
/h) systems is due to relatively higher capital costs of a lower capacity system.
However, increased variable costs, mainly attributable to annual membrane replacement, represent
the main extra expense of the ICFBMR system. It should be noted that the analysis assumes that the
ICFBMR uses approximately 25%less natural gas than the conventional SMR, but this saving is
more than offset by membrane replacement costs.
6.4 Discussion
The membrane flux characteristics (i.e. foil thickness) and the reactor operating conditions determine
the required membrane area. The membrane area is a key design parameter of the ICFBMR
configuration, as this controls reactor sizing and strongly influences both capital and operating costs.
Simulation shows that high reactor pressure (> -2,500 kPa) and low permeate pressure (< -100 kPa)
are the major reactor parameters that can be used to reduce membrane requirements. Increasing the
reactor temperature significantly reduces membrane area, but operating conditions are likely to be
governed by maximum allowable membrane temperatures (<600C). There is a clear incentive to
develop high-flux (i.e. thin) membranes that can operate at higher temperatures and larger pressure
differentials.
Modelling suggests that the ICFBMR design is relatively tolerant to variations in feed preheat
temperatures and solids circulation. The amount of nitrogen internally circulated within the ICFBMR
does not significantly influence membrane requirements, indicating that there is little economic
benefit of using oxygen in place of oxidation air. This finding also tends to discount the financial
merits of incorporating oxygen-permeable membranes within the reactor, unless they were cheaper to
operate than an air compressor. However, if the non-permeate reactor off-gas was to be treated to
remove C0
2
for sequestration, oxygen addition might be attractive.
The 30 NmVh flowsheet predicts that relatively high system efficiencies (-69%, based on HHV) can
likely be achieved for small-scale H
2
production with the ICFBMR design. As the required membrane
area and superficial gas velocity tend to make the reactor tall and narrow, minimization of the
membrane area is needed to obtain a practical design. In order to reduce the reactor diameter, it may
169
be desirable to reduce the downflow (annular) area of the ICFBMR. Study of alternate reactor
membrane layouts may be useful to determine the effect on solids circulation.
Table 6.5 presents several figures of merit for the 30 Nm
3
/h ICFBMR unit compared to a large-scale
and small-scale conventional SMR system. The ICFBMR system efficiency compares favourably
with conventional SMR systems. The relative reactor volume of the ICFBMR is significantly larger
than for a conventional SMR primary reformer. However for a fairer comparison, the volume of the
shift reactors and PSA should also be included in the conventional SMR values.
Table 6.5: Figures of merit for 30 Nm
3
/h H
2
ICFBMR and conventional SMR production units
Figure of merit Large-scale
conventional SMR
Small-scale
conventional SMR
(NAE, 2004)
Proposed 30 NmVh
ICFBMR design
H
2
:CH4 molar ratio 2.5 1.91 2.48
Overall thermal
efficiency
70-80%(steam export)
-60%(no steam export)
56%(incl. power, no
steam export)
80%excluding power
69%including power
Catalyst
productivity
-3,000 NmVh H
2
/m
3
(primary reformer only)
500 NmVh H
2
/m
3
Reactor
productivity
-1,000 Nm
J
/hH
2
/m
J
(primary reformer
furnace only)
375 NmVh H
2
/m
J
Membrane H
2
productivity
N/A N/A 13 NmVh m
2
Estimated H
2
cost
with capital
recovery ($CAD)
$1.62/kg
(267,000NmVh, Table
E-19, NAE, 2004)
$4.12/kg
(222 NmVh, see
Appendix 6.3)
$6.73/kg
(30 NmVh, see
Appendix 6.3)
The economic analyses clearly demonstrate that the capital and operating costs of membranes are
significant. Reducing the initial capital cost of the membranes is important, but membrane longevity
may be a more important cost factor. If membranes can be shown to operate for two or more years,
the ICFBMR unit economics improve significantly.
Finally, it should be noted that the hydrogen produced in the ICFBMR has the potential to be of
higher purity than H
2
produced from a conventional SMR system. A cost premium for the membrane
hydrogen may be warranted.
170
Chapter 7. Conclusions and Recommendations
7.1 Conclusions
The main objective of this study was to evaluate the ICFBMR concept for production of high-purity
H
2
to serve the emerging distributed H
2
market. Although the results from the pilot plant work were
somewhat below expectations due to catalyst performance and the limited installed membrane area,
the potential for the ICFBMR to supply fuel-cell quality H
2
from a small-scale ATR process has been
demonstrated. Some specific achievements and conclusions from this study:
Double-sided planar membranes using 50-um thick palladium alloy foil (25%silver) were
successfully prepared using proprietary techniques of Membrane Reactor Technologies Ltd
(MRT). Sievert's Law could be used to characterize the panel membrane flux. The calculated
active permeation area of the membrane panels was a fraction (from VA to VA) of the panel
permeation geometry. Post-run analysis suggest that the reduction in permeation area was likely
due to inter-diffusion of the palladium foil with the stainless steel substrate. MRT has
subsequently improved their process for depositing the inter-diffusion barrier.
There were no significant membrane failures during the 14 days of hot operation in the fluidized
bed pilot reactor. High-purity hydrogen was produced (>99.999%H
2
, excluding N
2
) from the in-
situ membranes for the first 180 hours of pilot testing. Although several small leaks developed,
all of the membranes survived the reactor testing intact (up to 650C with no protective covers),
and relatively high quality hydrogen (-99.8%dry basis, excluding N
2
) was produced for the
remainder of the pilot testing. Traces of steam were also likely present in the permeate H
2
at the
end of the testing, but this was not measured. No decrease in permeation was seen in the
membranes, despite heavy deposits of catalyst on the membrane surface.
Catalyst solids were proven to internally circulate up the reformer core and down the annulus in
both the cold model and hot pilot reactor. Results from cold model testing indicate that the solids
flux increases proportionally to the main gas feed flow the core to a superficial velocity (U
core
) of
-0.3 m/s, and that the solids flux levelled off at superficial velocities above -0.5 m/s. It is
postulated that this levelling was due to a gradual transition from bubbling to turbulent
171
fluidization. The addition of a small amount of secondary air to the bottom of the annulus
increased the solids circulation significantly.
Cold model testing showed that communication slots are required between the flow channels in
the membrane core in order to prevent maldistribution of gas and solids.
Solids flux correlations obtained from cold modelling closely matched the measured solids flux
in the pilot reactor, providing some confidence that dimensionless scaling of cold model data to
reformer conditions is valid.
The estimate of the effective membrane area during the pilot reforming tests with no N
2
-sweep
was close to the actual permeation area. This suggests that the "effectiveness"of the membrane
area was close to 100%. The N
2
sweep enhanced H
2
permeation, but was not as fully effective as
predicted from modelling,
The reformer was successfully operated under both SMR (external heating only) and ATR (direct
air addition) conditions. The reactor operation was very stable. Six membrane panels were
installed in the pilot reactor, less than half the full complement, and as a result, the reactor
performance was very much flux-limited. The maximum measured permeate hydrogen
production was 1.06 NmVh at 589C. The highest measured H
2
recovery was 1.17 Nm
3
/Nm
3
of
natural gas feed. The reactor was operated up to 650C, but low catalyst activity hindered reactor
performance. As expected, H
2
production increased with increasing temperature and lower
permeate H
2
partial pressure. The overall reactor performance could be adequately simulated with
a simple equilibrium model coupled with a permeation equation.
Helium tracer studies in both the cold model and hot pilot reformer indicated that only a portion
of the gas in the upper reactor (-10%) is circulated to the reactor core with the returning solids.
This ensures that only a portion of the nitrogen in the oxidation air reaches the permeation zone.
This was confirmed in ATR testing, where it was found that air addition to the top of the reactor
had little effect on the hydrogen flux, indicating that the ICFBMR system requires less membrane
area than a well-mixed ATR reactor using air. It also suggests that the ICFBMR system operating
with air can have similar membrane area as ATR reactors using oxygen or oxygen-permeable
membranes.
The deactivation of the NiO on alumina SMR catalyst initially used in the pilot reactor was not
unexpected, as this material is known to be intolerant of the cyclical oxidizing conditions present
172
when air is fed to the reformer. However, the poor performance of the novel ATR was a
disappointment, and curtailed the pilot plant program. The cause of the low ATR catalyst activity
is not known, as there was a non-analysis agreement in place for this material.
A commercial simulation program (HYSYS) was used to create a model of the ICFBMR based
on a series of equilibrium reactors. The effect of the main process variables on reactor
performance was investigated. When coupled to cold model solids flux correlations, the model
shows that the ICFBMR geometry permits enough solids circulation to match the thermal
demand of the reforming reaction with direct air addition (ATR).
Simulation of a 30 NmVh H
2
ICFBMR production system indicated that high thermal efficiencies
could potentially be achieved. Economic analysis suggests membrane cost and membrane
longevity are key areas for the viability of this process.
7.2 Alternative Reactor Applications
Membrane reactors tend to be flux-limited, and thus the required membrane area governs the reactor
geometry. This results in a larger solids volume than required for catalysis. Higher flux membranes
would reduce the reactor volume, lowering reactor, metal and catalyst costs.
Distributed reforming using a natural gas feedstock may not meet long-term environmental goals.
However, it is likely that novel autothermal reforming technology, of which ICFBMR is an example,
will play a role in the transition to a hydrogen economy. In addition, this technology can likely be
applied to alternative methane sources that are "greener"than natural gas, such as anaerobic digester
gas. It is also possible that higher hydrocarbons (C 3+) can be successfully reformed in this reactor
configuration. The ICFBMR continually moves catalyst between reforming and oxidation zones,
which may alleviate coking problems that can occur when reforming higher hydrocarbons in
conventional fixed bed reactors.
Another possible variation on the ICFBMR reformer is sorption-enhanced reforming (SER), where
calcium-based solids, such as limestone or dolomite, are used to capture C0
2
from the reforming
zone. Recent experimental work at UBC (Johnsen et al., 2006) showed experimentally the potential
for SER to be carried out in a bubbling bed reactor to produce relatively high-purity hydrogen. This
concept could be extended to a fluidized bed membrane reformer, where both C0
2
and H
2
removal
from the reforming zone would shift the thermodynamic equilibrium. C0
2
could then be separately
removed from the calcium solids in a separate calciner or calcining zone. A schematic of a possible
173
configuration is presented in Figure 7.1. Absorption of C0
2
is exothermic, which would help supply
most or some of the reforming heat. Heat, and perhaps stripping steam, would be added to the
calciner to desorb C0
2
. The bed solids, a mix of SMR catalyst and C0
2
-sorbent, is continually
circulated between the beds. A C0
2
-rich stream is produced for sequestration. A similar configuration
using an external solids circulation loop was proposed by Prasad and Elnashaie (2004). This SER
concept highlights the unique ability of fluidized beds to move heat and solids from separate reaction
zones.
Calciner
(C02 desorption)
| Heat
-|CQ2/Stearrj>
-| Off-gas >
/
P "
CaC03,
Catalyst
1
1
i , ,
, H2f
Membranes '
llllilli
CaO,
Catalyst
Bed surface
Reformer
(SMR reaction, H2
separation and
C02 absorption)
H2 >
j Steam ;>
|CH4/Steam>
Figure 7.1: Sorption-enhanced ICFBMR concept
In this study, the ICFBMR has been applied to high-purity hydrogen production from steam methane
reforming. One could also envision applying this fluidized bed membrane system to a number of
other high-temperature catalytic processes, such as propane dehydrogenation, where hydrogen needs
to be removed and heat transfer is important.
7.3 Recommendations
The follow areas merit further study:
Reactor Geometry:
174
o Additional cold modelling to determine whether reactor sizing can be reduced (space-
time yield increased) by using different layouts (e.g. 2 chord returns instead of an
annulus).
o Optimization of feed distributors and catalyst return geometry,
o Side-mounted membrane flanges for ease of reactor assembly.
o Investigate the effect of other reactor geometries on the rate of solids circulation,
including reactor height and membrane spacing.
Membranes:
o Determine longevity of Pd membranes in a fluidized bed environment at varying
temperature and fluidization velocities (both covered and uncovered).
o Find long-term flux stability of membranes to ensure that palladium - substrate inter-
diffusion does not occur.
o Investigate whether membrane efficiency remains high when H
2
recovery is increased to
economically practical values.
Catalysis:
o Long-term testing of a fluidizable ATR catalyst.
C0
2
sequestration:
o Evaluate the application of ICFBMR to sorbent enhanced reforming.
Finally, it is re-emphasized that membranes remain the key to the successful development of any
membrane reactor. Although it is believed that the ICFBMR concept greatly facilitates the use of H
2
-
permeable membranes, without development of robust, high-flux, cost-effective membranes that can
tolerate the high temperatures and pressures in the reforming process, the ICFBMR concept will fail
to compete with conventional reforming processes.
175
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Appendix 1 - Introduction Details
Steam:carbon molar ratio
Temperature (C)
Figure Al . 1: Equilibrium methane conversion in SMR as a function of steam-to-carbon ratio and
temperature (pressure = 1,000 kPa, graph contours are lines of constant conversion)
Table A 1.1: Steps employing catalysts in SMR (Armor, 1999)
Operation Temperature (C)
1 Sulfur conversion (HDS) 290-370
2 H
2
S removal (ZnO) 340-390
3 Chloride removal (Alumina) 25-400
4 Pre-reforming 300-525
5 Steam methane reforming 850
6 High temperature water gas shift 340-360
7 Low temperature water gas shift 200
8 Methanation 320
9 NOx removal (ammonia, SCR) 350
Table A 1.2: SMR reactions with oxygen input (Abba et al., 2003 after Xu and Froment, 1990)
SMR reaction with oxygen addition Rate
RI CH
4
+ H
z
O <- CO + 3H
2 hi
R2 CO + H
2
0 C0
2
+ H
2
R3 CH4 + 2H
2
0 <-> C0
2
+ 4H
2
k
r3
R4 CFL, + 20
2
*+ C0
2
+ 2H
2
R5 CH
4
+ 1.5H
2
0-CO + 2H
2
0 k
r5
185
Table A 1.3: SMR reaction rates (Abba et al., 2003 after Xu and Froment, 1990)
Reaction rate equation
RI
r
\
=
^ri (PCH4PHIO 1 PHI ~ PHI PCO 1 K
EQL
) / K
R2
r
i
=
kr i(PQOPHIO 1 PHI ~ PHIPCOI 1 K
eq2
)/
K
R3 r
_ t / p p2 p 3 5_ p 05n IV- X( \ , 2
'3
A
>3V
J
CHA
1
HIO
1
H2
1
H2
1
C02 '
1
^ e q, \
1
^ e q,2 )
1N
~
R4
'4
N
-
R
4
A
CH4
A
02
R5
r -k r
0
'
5
Y
0 7 5
'5
A
'r5
A
C/ / 4
A
02
where K = 1 + K
co
P
co
+ K
H2
P
H2
+ K
CH4
P
CH4
+ K
H20
P
H20
1P
H2
Table A1.4: SMR reaction rate parameters (Abba et al., 2003 after Xu and Froment, 1990)
Rate/
adsorption
constant
Pre-exponent factor Activation energy / heat of
adsorption (kJ/mol)
Ki
8.34E17(molPa
us
/kgs) 240.1
kr2
1.22E1 (mol/kg s Pa) 67.1
k
r3
2.01E17(mol Pa
6
'/kg s) 243.9
k
r4
1.26E12(mol/kg s) 170.3
k
rS
3.08E10(mol/kg s) 139.7
K-co
8.23E-10 (Pa
1
) -70.65
K-CH4
6.65E-9 (Pa
1
) -38.28
KH20
1.77E5 (-) -88.68
KH2
6.12E-14(Pa"') -82.90
Keq.l
1.2E23(TV) 223.10
Keq.2
1.77E-2 (-) -36.58
186
Appendix 2 - Membrane Details
JM Base Pr i c e s Palladium From: J u l 1992
US$ Monthly Av er age To: Jan 2007
in*,
; ;
1992 I 1993 I 1994 I 199S I 1996 I 1997 I 1998 I 1999 I 2000 I 2001 I 2002 I 2003 I 2044 I 200S I 2006 I
Figure A2.1: Palladium pricing 1992-2007 (source: Johnson Matthey website)
187
SideB Side A
Side A
Panel #1
3/16"
tube
3/16"
tube
Side B Side A
lo ts o f
small
creases,
especially
o n LHS
Side B Side A
Panel #5
Panel #3
3/16"
tube
3/16"
tube
J
\
1
faint
crack
numero us
surf ace
bumps,
due to
alumina?
Side B
small '
crease
small
number o f
surf ace
bumps,
due to
alumina?
Panel #4
ladder-like
|marks faintly
visible fro m
substate
Side B Side A
Panel #6
Side B
Panel#8
Panel A is not shown, but was clear both sided
Figure A2. 2: Crease defects in membrane panels installed in I CF B MR
(after bonding, but before service in the I CF B MR pilot reactor)
188
Table A2.1: Permeation rig components
Tag Description Size/
Capacity
Model / Manufacturer
V-10 316SS pressure vessel 10"IDx25" Axton Manufacturing
H-10 Semi-cylindrical ceramic
fiber heaters (2)
3.5 kW/
240VAC
Watlow, model VS112A18
FIC-01 Feed mass flow controller 0-6 SLM H
2
Brooks, model 5850S
FIC-02 Sweep mass flow controller 0-2 SLM H
2
Brooks, model 5850S
FI-03 Permeate mass flow meter 0-1 SLM N
2
Omega, model FMA-A2306SS
FI-04 Rotameter (CHE3495A) Calibration in
figure below
Fisher-Porter
VP-10 Vacuum pump
l
A HP Fisher Technical, model LAV-3
Table A2.2: Gas chromatograph details
GC#1 GC#2
Application Permeation rig testing Permeate from ICFBMR
ICFBMR ROG testing pilot plant
Model Shimadzu GC-8AIT Shimadzu GC-8AIT
(CHE4116A) (CHE3577A)
Detector type TCD TCD
Detector current 60 mA 60 mA
Sample introduction Automatic sampling valve Syringe injection (0.1 m)
Column Hayesep DB 30' x 1/8"OD, Supelco 15' x 1/8"OD, Carboxen
100/120 mesh, Lot 154 1000, Lot 080797
Injector temperature 150C 110C
Column temperature 120C 100C
Carrier / reference gas Argon Argon
Carrier / reference flow 22 / 33 ml/min
Integrator Shimadzu CR601 (CHE4116B) Shimadzu C-R3A (CHE4116B)
Integrator settings
Width 5 5
Slope 29.76 15
Drift 0 0
Chart speed 4 mm/min 6 mm/min
Min. area 1 100
Tvpical gas factors
H2 3.9min/3.643E-05 3.86 min/3.9302E-5
N2 4.52 min / 4.820E-04 4.52 min / 6.859E-4
CO 4.78 min/3.567E-04 4.78 min/4.706E-4
CH4 6.29 min / 1.326E-04 6.28 min / 1.441E-4
C02 8.95 min / 4.632E-04 8.84 min / 5.036E-4
189
Table A2. 3: Hydrogen permeation data for Panel A - effect pf hydrogen partial pressure
Data
point
Permeation vessel conditions Sweep
argon
(SLM)
Permeate
pressure
(kPa)
H2flux
(SLM)
[H2] in
permeate
(vol%)
Permeate
H2 partial
pressure
(kPa)
Sq. root
H2 partial
pressure
(Pa
A
0.5)
Data
point H2 feed
(SLM)
Temp (C) Pressure
(kPa)
H2 partial
pressure
(kPa)
Sweep
argon
(SLM)
Permeate
pressure
(kPa)
H2flux
(SLM)
[H2] in
permeate
(vol%)
Permeate
H2 partial
pressure
(kPa)
Sq. root
H2 partial
pressure
(Pa
A
0.5)
N
o
s
w
e
e
p
1 3.0 549 134 134 0 101.3 0.78 100% 101.3 47.5
N
o
s
w
e
e
p
2 6.0 543 170 170 0 101.3 1.41 100% 101.3 94.5
N
o
s
w
e
e
p
,3 6.0 549 205 205 0 101.3 1.91 100% 101.3 134.4
S
w
e
e
p
g
a
s
4 6.0 543 170 170 0.40 101.3 1.88 83% 83.6 123.6
S
w
e
e
p
g
a
s
5 6.0 543 170 170 0.67 101.3 2.03 75% 76.2 136.7
S
w
e
e
p
g
a
s
6 6.0 543 170 170 0.93 101.3 2.10 69% 70.1 148.1
S
w
e
e
p
g
a
s
7 6.0 543 170 170 1.20 101.3 2.15 64% 65.0 157.9
V
a
c
u
u
m
8 6.0 548 170 170 0.0 67.5 2.26 100% 67.5 153.1
V
a
c
u
u
m
9 6.0 548 170 170 ' 0.0 50.5 2.70 100% 50.5 188.0
V
a
c
u
u
m
10 6.0 548 170 170 0.0 33.6 3.18 100% 33.6 229.5
Table A2.4: Effect of temperature on permeation for Panel A
(pure hydrogen in permeation vessel, no sweep gas to permeate)
Temperature
( C)
Measured H2 flux (SLM) Permeate
pressure
(kPa)
Temperature
( C) Vessel pressure
Permeate
pressure
(kPa)
Temperature
( C)
238 kPa 307 kPa 376 kPa
Permeate
pressure
(kPa)
455 1.39 2.06 2.64 101
502 1.76 2.42 3.03 101
538 1.85 2.61 3.32 101
564 1.91 2.71 3.53 101
Table A2.5: Effect of temperature on permeation for Panels 1-8 (pure hydrogen in permeation vessel,
no sweep gas to permeate, vessel at 300 kPa, permeate at 101 kpa)
Panel 1 Panel 3 Panel 6
Temp ( C) Flux (SLM) Temp ( C) Flux (SLM) Temp ( C) Flux (SLM)
463 1.44 463 1.14 463 0.93
483 1.53 485 1.20 532 0.96
505 1.74 503 1.39 545 1.03
536 1.87 536 1.53 570.5 1.17
555 2.02 554 1.69
Panel 4 Panel 8 Panel 5
Temp ( C) Flux (SLM) Temp ( C) Flux (SLM) Temp ( C) Flux (SLM)
463 0.69 450 1.14 463 1.69
515 1.07 450 0.99 482 1.77
537 1.13 474 1.21 507 2.13
547.5 1.25 505 1.42 536 2.23
568.5 1.45 530 1.52 555 2.42
544 1.51
191
Appendix 3.1
Cold Model Installation Instruction
Figure A3.1.1 presents a schematic of the cold model and include part numbers listed in the
instructions below. Wear appropriate personal safety protection.
1. Disassemble full column:
Drain catalyst from column a nozzle on the lower column section
Close return standpipe valves <1>
Disconnect return standpipe from column <2>
Remove main 6"feed pipe <3>
Unbolt and remove windbox <4>
Remove lower 4' column section
2. Install internals:
Assemble empty core box
o Remove all panels <5> from the core box <9>
o Insert VS" location tube <11> through top of box. This tube is about 11"long so as to
fit in the column and will act as the guide to the Vi" rod <10>, which secures the core
box.
o Install
l
A" filter impulse connections <23> onto core box channels
o Locate box <9> on the floor directly under the 12"column
Feed rope <17> from 2"angled nozzle <8> at the top of column through to the open bottom
and tie to middle of VS" box support tube <11>
Feed Vi" plastic impulse connection lines <from upper column ports through open bottom of
12"column, ensuring that they are not tangled
Connect impulse lines to the appropriate impulse filters <23> on the core box <9>
Tie wrap impulse feed lines <18> as needed
Lift / raise box into the column in increments:
o Always tie off support rope <17>
o Pull slack of Vi" impulse tubes <18> through the connection ports on column wall
o Ensure impulse lines <17> are not tangled
Secure box support by inserting 3/16"hanging tube <10> through VS" support tube <11> and
through the external Plexiglas bosses. Secure 3/16"tube with Swagelok port connections
<12> to NPT drilled bosses
Center and level core box with Vi" lateral tubes <21>, both east-west and north-south and
secure with Swagelok fittings <22>
Pull final slack of Vi" impulse lines <18> and seal Swagelok fittings on column wall
Pull rope <17> tight and secure to the inside of the column nozzle <8> so as to permit the
internals to be lowered during disassembly
Slide in the core box panels <5> from the bottom and secure in place
3. Install oxidant feed line
Insert a Vi" steel guide through the column with the opposing port connections
Push the 3/16"oxidant distributor <6> over one end of the Vi" guide and feed the distributor
through the column to the opposing port
192
Secure the distributor with Swagelok port connections <7> to the Plexiglas bosses on the
column wall
Attach distributor to oxidant feed line
4. Install secondary feed distributor:
Center, and secure distributor <16> in each of the four quadrants
Secure
l
A" distributor feed lines <15> with Swagelok port connections <14> to Plexiglas
bosses
Attach both distributor feed lines <15> to building air supply
5. Install windbox:
Last check of internals
Make sure the two distributor plates <20> are oriented so the drilled holes in the plates match
Lift and bolt the windbox <4> to the column, ensuring that the square feed hole pattern
matches the orientation of the core box <9>
Reattach the 6" feed line <3> to the windbox <4> and to the flexible connection on the
building air supply
6. Solids addition:
Add a small flow of gas to distributors to reduce solids back sifting and aid bed settling
Remove the steel exit elbow <13> on top of the column
Using a funnel, fill the column with F CC until the settled bed level is 25 mm above the core
box <9>
Reattach steel exit elbow <13>
7. Instrumentation:
Connect V" impulse lines <18> to appropriate pressure transmitters <19>
With no gas flow to column, check the calibration of the pressure transmitters <19> on the
data acquisition computer and zero if necessary
8. Column disassembly:
Drain solids from column via nozzle near bottom of column
Remove main 6" feed pipe <3>
Unbolt windbox <4> and remove remaining solids - this can be messy
Remove secondary distributor < 14-16>
Remove oxidant distributor <6-7>
Remove core box panels <5> by unbolting setscrews at the bottom of the box <9> assembly
Disconnect impulse lines <18> connected to core box <9>
Open 2" angled nozzle <8> near top of column and tie off the rope <17> attached to the core
box
Remove the 3/8" tube <10> securing the core box to the column
Using the rope <17>, slowly lower the core bolt out the bottom of the column
193
<13> exit no zzle elbo w
Cyclo nes
<17> ro pe to raise co re bo x
<8> angled no zzle (2")
<7> o xidant fitting (2)
<6> 0.375" o xidant distributo r
12> co re bo x suppo rt fitting (2)
<10> 0.375" co re bo x suppo rt ro d
<11>14" co re bo x lo catio n tube
<16> seco ndary distributo r (4)
<14> 2 distributo r fitting (2)
<15> %" distributo r f eed
<20> distributo r plates
<1> cyclo ne return
valves
V
V
<2> standpipe return
^ P T ^ <19> pressure
transmitters
<18> V*" plastic impulse tubing
<9> Plexiglas co re bo x
<23> pressure filter fitting (many)
<5> co re panels (8)
<21 > VA" centering tubes (6)
<22> centering tube fitting (6)
<3> main f eed pipe (6")
Figure A3. 1. 1: Cold model assembly schematic
194
Appendix 3.2 - Cold Model Testing Details
6.35
/To p
distr
typ' "I T / plate
5 8
_ ^ L_ / distributo r
^ . 38 pm
II i i II M II l i , I
" 6 4 _J L_ \ Bo tto m
6.35 ? .1 I distributo r
W Section A-A plate
(all dimensions in mm)
Figure A3. 2. 3: Cold model main distributor plate
Oxidant
feed
-182-
Settled bed depth
of FCC particles
75
50
25
r
Oxidant distributor
(12 mmOD, 2x13 holes,
1 mmdiam)
Oxidant
I feed
To p of core box
Co lumn shell
(285 mm ID)
Figure A3. 2. 4: Elevation view of cold model oxidant distributor (all dimensions in mm)
196
Table A3.2.1: Cold model feed air rotameters
Tag Service Scale Model Material
FI-OT Main air feed (1) 0-600SLM air Omega FL-1658-SS Glass body, SS float
FI-02 Main air feed (2) 0-236 SLM Omega FL-1656-SS Glass body, SS float
FI-03 Secondary air
feed
3-30LPM air Cole Parmer
U-32461-56
Acrylic body, SS float
FI-04 Oxidant air 30-280LPM air Cole Parmer
U-3 2461-64
Acrylic body, SS float
re
Q.
OL
3
Si
- 1
a
1
c
"55
0 A-
0 100 200 300 400 500 600 700
Air Flow (SLM)
Figure A3.2.5: Pressure drop over cold model main distributors
800
o Sec ondary (per tube)
Oxidant
0 <!>-
20 80
Fi)
40 60
Air flow (SLM)
;ure A3.2.6: Pressure drop over cold model secondary and oxidant distributors
100
197
Table A3. 2. 2: Cold model pressure transducer data
Description Type Tag Channel Calibrated full
scale range (kPa)
Over main distributor plate Pd 18 20 14.8
Bottom of North Quadrant
Pg
5 11 15.6
Freeboard (c/w atmosphere) Pd 1 6 3.2
Core bottom channel 4 (c/w atmosphere) Pd 6 0 14.9
Core bottom channel 5 (c/w atmosphere) Pd 13 21 96.9
Core mid channel 1 Pg
12 1 96.5
Core mid channel 2
Pg
23 3 16.0
Core mid channel 3
Pg
14 15 15.9
Core mid channel 4 Pg
9 13 15.9
Core mid channel 5
Pg
8 7 14.8
Core mid channel 6
Pg
7 9 15.8
Core mid channel 7
Pg
22 2 15.6
Core mid channel 8
Pg
4 5 16.4
Core top channel 4 (c/w freeboard)
Pg
0 4 3.2
Core top channel 5 (c/w freeboard) Pd 17 17 3.1
Core top channel 6 (c/w freeboard) Pd 16 12 3.2
Note: Pd = differential pressure, Pg = absolute pressure, c/w = connected with
routed up south
quadrant
Figure A3. 2. 7: Plan view of cold model.pressure tap connections with vertically slotted panels
198
Freebo ard ^@
(Elev 2090)
To p co re channel (5) (^)-
Mid co re channels (1,3,5,7) (&^>
Bo tto m co re channel (5) (@^
Annular sample
po ints (4)
(elev = 325)
No rth quadrant ^gg
(elev = 70)
Windbo x
Co re
bo x
Windbo x
Elevatio n view lo o king East
All dimensio ns in mm
(^) To p co re channels (4,6)
Mid co re channels (2,4,6,8)
{ ) Bo tto m co re channel (4)
To p co re
pressure taps
(elev= 1494)
Mid co re
pressure taps
(elev = 862)
Bo tto m co re
pressure taps
(elev = 230)
Distributo r (elev
= 0)
Figure A3. 2. 8: Elevation view of cold model pressure tap connections (looking east)
199
0 0.0025 0.005 0.0075 0.01 0.0125 0.015
Velocity (m/s)
Figure A3.2.9: Cold model pressure drop vs. superficial air velocity for SMR (NiO) catalyst
2.0
1.5
Q.
Q.
O
D 1.0
0
3
co
Q)
0.5
A
A
/ A A A A A
A /
A f
A /
7
A increasing flow
decreasing flow
r Umf = 0.0030
0.0
0.0000 0.0025 0.0050 0.0075 0.0100
Superficial velocity (m/s)
Figure A3.2.10: Cold model pressure drop vs. superficial air velocity for ATR catalyst
200
120
0
0 20 40 60 80 100
Rotameter Reading (bottom ball)
Figure A3. 2. 11: Calibration of FI-06 used for helium injection in cold model testing at 207 kPag
as measured against a mass flow meter operating with helium
12
0.35 0.40 0.45 0.50 0.55
Si gnal (volts)
Figure A3. 2. 12: Typical calibration curve of thermal conductivity detector (TCD) with helium
used in cold model system (TCD #2 on 050426, xlOO amplification)
201
9
7
O '
>
c
s
*
(0
3
cr
c
? 3
x
re
1
0
Figure
x
x
x
x
x
x
x x
X X
X
X
X
X
X
X
X
M
X
X
X
X
X
X
x
x
x
*x
&X
X
X
X
X
X
*x
X
100 200 600 700 300 400 500
Main air flow (SLM)
A3.2.13: Ratio of maximum to minimum quadrant solids velocity for cold model data
800
(0
Q.
J
Q .
O
<u
3
(A
(A
d)
Q .
- 7
0)
c
c
ra
xz
O
horizontally slotted panels
y = -0.0027X + 8.77
R
2
= 0.994
A
30 SLM annular air
20 SLM annular air
O 10 SLM annular air
- Linear (20 SLM annular air)
100 200 300 400 500
Main Feed (SLM)
600 700 800
Figure A3.2.14: Pressure drop over channel 4 in cold model core with horizontally slotted panels
(95% confidence interval)
202
94 SLM main air
Frequency (Hz)
0 2 4 6 8 10
Frequency (Hz)
236SLM main air
0 2 4 6 8 10
Frequency (Hz)
236SLM main air
0 2 4
Frequency (Hz)
480SLM main air
0 2 4
Frequency (Hz)
480SLM main air
0 2 4 6 8 10
Frequency (Hz)
2 4 6 8 10
Frequency (Hz)
800SLM main air
0 2 4 6
Frequency (Hz)
713 SLM main air
0 2 4 6 8 10
Frequency(Hz)
(a) Solid panels (b) Vertically slotted panels
Figure A3.2.15: Gage pressure at mid4ieight of cold model channel 4, 20SLM air to annulus
203
12.07
10.0 -! 1 . 1 : !
10.0 10.5 11.0 11.5 12.0 12.5
Corrected pressure in bottom of channel 4 (kPa)
Figure A3.2.16: Pressure of annulus vs. channel 4 pressure in cold model with vertically slotted
panels (corrected for elevation difference)
204
Figure A4. 1. 1: I CF B MR main distributor drilling pattern
200
CL
^ 150
Q.
O
o 100
a)
i _
3
tn 50
o
i_
CL
0 i
A
A
A oxidant
annular
main
0 20 40 60 80
Air flow at ambient conditions (SLM)
Figure A4. 1. 2: I CF B MR pressure drops for three gas distributors
100
205
206
NOZZLE SCHCDUL C
Figure A4.1.4: I CF BMR external pressure vessel drawing (1)
Figure A4.1.5: ICFBMR external pressure vessel drawing (2)
w . f t * a s t a u ; s
AX row
7 . ft
J / L L Of MATERIAL S
i\ )/< I ii iff V r w r t ft) ?/r* 'ma to tmT~
* 7542A03
j f t ' - t f t n c w r i n wo t .
)/f-11UNC. il/t-UXiriaHig:
S i n BAI w a o s ra > y
' OA sureKHcip dt w u w w ; yuam.
I 1 I ) B L O C K T H I C K N E S S A N D C A P F R O M S A * B L A D E T H I C K N E S S .
I 1 2 ) B O R E D t A U E T I R T O W A T C H 0 . 0 . O F 3 * N P S P F E .
I 1 3 ) R E M O V E A L L 8 U R R S A N D S H A R P E D G E S . R O U N D O F F S H A R P C O R N E R S .
I 1 4) F O U R (4) C A S T E R S e / M O U N T I N G H A R D W A R E S U P P U E D B T N OR A M .
CD 5 ) A L L F I L L E T W E L D S T O B E V M I N I M U M U N L E S S O T H E R W I S E N O T E D .
CD 6 ) Aa I T E M S T O B E P R E P A R E D A N D P A I N T E D . I N S T R U C T I O N S T O F O L L O W .
I I 7 ) M A X I M U M D E S I G N L O A D - 7 0 0 0 l b s .
8 ) T R W . m V E S S E L T O F R A M E P R I O R T O S H I P P I N G .
I ' Sf fit. 5X'
M 1
C L E A N I N G k P A W T W C :
S U R F A C E P f t F P . - S U R F A C E S M U S T B E C L E A N A N D F R E E
O F L O O S E R U S T , M I L L S C A L E . D E T E R I O R A T E D P R E V I O U S
C O A T I N G S . D I R T , O R , G R E A S E A N D C H E M I C A L C O N T A M I N A N T S .
A B R A S I V E B L A S T I N G S R C D M U E N D E D .
P R I M E R - ( 1 ) C O A T 7 0 6 9 R E D P R I M E R .
F J N J S t J - I N D U S T R I A L E N A M E L . G R E Y C O L O U R . F O L L O W
M A N U F . I N S T R U C T I O N S F O R C O V E R A G E .
< f Q 0 T | r C A W - E71T-1
(l-D)GMAW => ER70S-6
iVWvfACTUKD 1:
N O R A M E N C W E E R 1 N G A N D C O N S T R U C T O R S L T D .
f o r
U B C I C F B M R
I N T E R N A L C I R C U L A T I N G F L U l D I Z l N G B E D
M E M B R A N E R E F O R M E R
M O B I L E S U P P O R T F R A M E D E T A I L S
Figure A4. 1. 6: I CF BMR support steel drawing
Figure A4.1.7: ICFBMR internal vessel drawing (1)
Figure A4. 1. 8: I CF BMR internal vessel drawing (2)
Figure A4.1.9: ICFBMR main distributor mechanical drawing
V COIL A (9 TURNS)
H' COIL 8 (9 TURNS)
H"COIL C (9 TURNS)
NOZZLE SCHEDULE
KSM MPS SCM IfWWC
DESIGN CODES AND SPECIFICATIONS
VESSEL aw. BE OESICWD A M FABROIED IN ACCORDANCE fir*
- ASK Ml D(V 1. 7001 EDITIOH.
- U" STA* REOD.
DESIGN CONDITIONS
CONTEXTS: PROCESS CAS k WIROCEN SwfEP
SPECK CRAW. 0.01
UTERKAL OESCN PRESSURE 0 TEltfEJWWtE: 50) PStt I WOT
ECTDBW DESKN PRESSURE 4 TEMPERATURE 15 PSK O MOT
ommcPRESSURE TEKPGUTIME:
CO P9C O 4C0T
UMHJM C O O HP* TEMPERATURE: 3J T SCO rac
RADWOWItt: N01 JKT0 ASPER UH*-J3(B) MC W-11(c)
OMRCr M T TESTMCi NOT KE0TJ AS PER U*-5l(BHlXl>) AND W3-M(a)(lXb)
POST QJ> HEAT IKEArUENT: MOT urnsAS pa uai UCS-MNOTE p) w m-iotooXd)
CORROSOI mcnfHS: NONE
0E9CN M) SPEED: NOT A OESCN ffiOUREMENT
SEKWCr NOT A OtSCN REOUWEVENT
MATERIALS OF CONSTRUCTION
SfCLL: SAt yon B. SEAMLESS PIPE
KAft SAW GRADE iPB PFE CAP
NOZZLE: SAiDJ SEAMLESS Ftft (PER SOCDULE)
FIANCES.' SA-105(EXCEPT AS NOTED)
REPADS: N/A
SUPPORTS N/A
MIFJQW. ATOMS;
SA KI CRADE A
EITERWL FTTTMS: SA 202 GRADE A
VAMMr OC: SA-105
STUDS / NUTS SA-1H-B7 / SA-1M-JH
CASKETS: CtLON JStO
WEIGHT, CAPACITY &AREA
GENERAL NOTES
i
NORAM
PROirct MD ?(MM DATE
INTERNAL CIRCULATING
FLUIDIZED BED MEMBRANE REFORMER
UBC ICFBMR
3 COIL CAST PREHEATER BLOCK
2
rwrcufn
APPtKWEO EOT TEW [t-W IIIV-
N.T.S. 1 1 OF 1 | ZO845-40OJ | A
Figure A4.1.10: I CF BMR internal preheater
Al l dimensions in mm
Material : 304L SS
VA Swagel ok nuts wel ded
to the box to hold support
guide from upper flange
r
2. 7-
CD
OO
83
88
V
V
CN
Pl an view Elevation
Figure A4. 1. 11: I CF B MR draft core box
214
1407
305
Dummy
305
Membrane
22-
63.50 305
Membrane
64 305
Membrane
View 1: Membrane assembly
before sealing strips
Membrane
co nnecto r (part 2)
1524
1422
r
Dummy Membrane Membrane Membrane
Co re draft box
View 2: Membrane assembly
with sealing strips
Six co mmunicatio n slots (57 x 22 mm)
Part C: Membrane backing strip
(graphite gasket underneath)
Figure A4.1.12: Membrane assembly general arrangement (dimensions in mm)
0.50-H
Part 3 - 4 Req'd
304/316SS (%" Thick)
Note: Faces do not need to be machined
Figure A4.1.13: Dummy membrane panel (all dimensions in inches)
3.25-
1/8" thick 304 SS
8x3/16" thru'
C - 8
backing
strips
'/ thick 304 SS
16x3/16" thru'
0.1875--j--
0. 1875-|
D -1 dummy panel
No tes:
All SS materials supplied
All dimensio ns in inches
Dims to ho le centres
2.875
Figure A4.1.14: Membrane backing strips and full-length dummy panel (all dimensions in inches)
217
CO
82. 55
| Part 2 - Connector Piece (4 Required)
o>
No tes:
1. All dims are inches
1. Man 316 o r 304 SS
3. 3Wx ZV* sheet supplied
UBC Chemical & Bio lo gical Engineering
No tes:
1. All dims are inches
1. Man 316 o r 304 SS
3. 3Wx ZV* sheet supplied
I C F BM R Me mb r a ne C o nne c to r Pi e c e
Designed /Drawn By: T. Bo yd
SIZE
A
FSCMNO DWG NO
ICFBMR-CNT-001
REV
B
DWG NO
ICFBMR-CNT-001
REV
B
Date: No v. 18. 2003
SCALE 1:1 | [SHEET 3 OF 16
Figure A4.1.15: Membrane connector piece (all dimensions in mm)
218
P U R O C W I R O C C N S W E E P U r m O C E N
t
5
M O T E S :
1 . E S D - E M E R G E N C Y S h V T D O W N .
NORAM MEMBRANE REACTOR Techno lo gies
U.B.C PILOT PLANT
CYLINDER SHED / GAS COMPRESSOR
KTS 1 10F3 1 D-Z0MS-H11 1 A
Figure A4.1.16: P&I D for pilot plant (gas cylinders)
N O T E S :
1 . ' C C " D E N O T E S C O N N E C T I O N T O C A S C H R O M A T O G R A P H
2 . A L L T U B * I S I / * " S S S W A C O . O K U N L E S S O T H E R W I S E N O T E D
3 . R U P T U R E D G K R A T E D 3 5 0 P S B O2TC. 2 5 0 P S l C O 1 W C
NORAM MEMBRANE REACTOR Technologies
U.B.C PILOT PLANT
FEED SYSTEMS
Figure A4.1.17: P&I D for pilot plant (feeds and condensers)
Figure A4.1.18: P&I D for pilot plant (external preheater)
222
Table A4.1.1: ICFBMR thermocouples
Tag Location Measurement location Tag Location
A B C D
TE-114 Annulus (quadrant 1) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-115 Annulus (quadrant 2) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-116 Annulus (quadrant 3) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-117 Core (channel 1) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-118 Core (channel 4) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-119 Reactor freeboard 25mm above
core box
152 mm above
point A
152 mm above
point B
X
Table A4.1.2: ICFBMR pressure transducers
Tag Service Model Range
DP-01 Differential pressure in reactor (various points) Omega PX750 0-2.54 m WC
DP-02 Differential pressure in reactor (various points) Omega PX750 0-2.54 m WC
PT-121 Outer reactor (V-01) pressure (gauge) Omega PX182 0-3,449 kPa(g)
PT-272 Inner reactor (V-02) pressure (gauge) Omega PX503 0-2,069kPa(g)
Table A4.1.3: ICFBMR pressure tap and sample points
Tag Service / Location Filter on tip?
PT-A Freeboard, 150mm below top flange No
PT-B Splash zone, 140 mm above core box Yes
PT-C Adjacent to oxidant distributor Yes
PT-D Top of center flow channel Yes
PT-E Mid4ieight of center flow channel No
PT-F Bottom of center flow channel No
PT-G Annular quadrant 3 top - 127 mm below top of core box No
PT-H Annular quadrant 3 bottom - 127 mm above bottom of core box No
PT-I Annular quadrant 1 top - 127 mm below top of core box Yes
PT-J Annular quadrant 1 bottom - 127 mm above bottom of core box Yes
223
4 point annular
thermo co uples (3)
TE-114/115/116
3 point splash zo ne
thermo co uple
rm
4 point co re
thermo co uples (2)
TE-117/118
TC point C
TC point B
TC point A
TC point D
PT-A
TC point C
TC point B H
TC point A
Figure A4.1.20: I CF B MR instrument locations
224
Table A4. 1. 4: Equipment list for I CF B M R pilot plant
Tag Name Size Materials Description
C-1 Gas compressor 50SLM at 20MPa
- Fuelmaker model P30
DSU Desulfurizer vertical cylindrical vessel 0.65m
x0.1m OD
SS vessel Cylindrical vessel filled with sulfur adsorbant
(CalgonSulfasorb-8 activated carbon pellets
impregnated with 8%copper oxide, mesh size 4x10)
DIU Deionizer 3 cylinders Fibreglass US Filter (activated carbon bed followed by 2 cation
exchange resin beds)
V302A/B Water pump 0.71mx0.11mOD 316 SS N2 padded vessels
E-1 Interchanger Shell: 1.22m x 0.22 OD 316 SS Rating 1.35MPa
E-1 Interchanger
Tubes: 6.2mm OD x2.4m 316 SS Area = 0.047 m2
E-2 Condenser Shell: 1.22m x 0.22 OD 316 SS Rating 1.35MPa
E-2 Condenser
Tubes: 6.2mm OD x1.2m 316 SS Area = 0.024 m2
E-3 External preheater Outer shell: 0.29m ID x1.52m CS Rating 1.64 MPa
E-3 External preheater
Inner shell: 0.1m ID x1.3m 316 SS Rating 1.28 MPa
E-3 External preheater
Heater: 2 x6 kW (240V) -
H-1 Internal preheater Block: Lead See equipment drawing
H-1 Internal preheater
Tubes: 3 tube coils 316 SS See equipment drawing
H-1 Internal preheater
Heater: 2 x 6 kW (240V) ceramic fibre 2xWatlowVS108A18T
H-2 Reactor heater A oriqinal: 2 x4.3 kW (240V) ceramic fibre 2x Watlow VS108A30S
H-2 Reactor heater A
revised: 2 x 5kW (240V) Incoloy tubes 2x WatlowRDN134J10S
H-3 Reactor heater B oriqinal: 2 x4.3 kW (240V) ceramic fibre 2 xWatlow VS108A30S
H-3 Reactor heater B
revised: 2 x 5kW (240V) Incoloy tubes 2xWatlowRDN134J10S
V-02 Internal reactor O.135/0.256m ID x2.31m 304/310SS See equipment drawings
V-01 External reactor 0.41 m OD x 3.64m overall CS See equipment drawings
tijl, Overview.cim
0
File View Help
to
Figure A4.1.21: ICFBMR pilot plant control screen #1
Figure A4.1.22: I CF B MR pilot plant control screen #2
Figure A4. 1. 23: I CF B M R pilot plant control screen #3
to
to
so
% FBMR. cim
File View Help
m
0
FEEDS r~~~F9MR
OFF-OAS
V-01 Pressure
[3453 Wag
PI-121
F B MR Pr essur e Ba l a nc e
13964kpa
T i . i i 3 h 372.0C
Oxidation Zone
TMio|i372.QtC
V-01
:
| j V-02
| ;
1372.0C
1-511 kpag
12(01/200514:58:29
HYDROGEN
X V- 131
-|1372.QC
1372.0oCTic-iQ9
P R E HE AT E D F E E D
TI-111
1372.0C
1372.0C
NITROGEN
FL UI D B E D A N N U L U S
1372.0C
1372.0C
1372.0C
1372.0C
T M 1 4
TI -11S
Tl - 116
TI-117
TE M P E R A TU R E
P R O F I L E S
P R E S S U R E T A P S
[3<Tl kpa
DPI-001
35.4
k
P
a DPI-002
[23.5 kpa s ma i i D P
0.S SLPM
1372.0C T i c - n o
OA S / S T E A M
Figure A4. 1. 24: I CF B M R pilot plant control screen #4
%, TRIPS, t.im
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O
j t YA WCOl *
["""FSR*"""
TRIPS TUNING,
ESDI TRIPS
PAHH305 1340.1 | -504.6
PAHH272 1349.9 | -4BS.9
PAHH202 1340.1 j -479.3
TAHH108 800.0 | 1372.0
TAHH109 i 600.0 1372.0
TAHH114A 6S0.0 [ 1372.0
TAHH114B 750.0 | 1372.0
TAHH114C S50.0 | 1372.0
TAHH1UD [ 6500 | 1372.0
TAHH115A | 650.0 | 1372.0
TAHH115B | 650,0 1372.0
TAHH115C | 725.0 | 1372.0
TAHH1150 675.0 1372.0
TAHH116A | 675.0 | 1372.0
TAHH116B | 675.0 1372.0
TAHH116C 650.0 1372.0
TAHH116D I 650.0 | 1372.0
ESD4 TRIPS
TAHH110 | 750.0 | .1372.0
TAHH220
TAHH225
TAHH230
TAHH235
ES D 2 T R I P S
- TAHH117A
TAHH117B
TAHH117C
TAHH117D
TAHH118A
TAHH118B
TAHH118C
TAHH118D
TAHH119A
TAHH119B
TAHH119C
TAHH111
TAHH112
TAHH113
E SD 5 TRIPS
1373.0 | 1372.0
400.0 21.5
650 0 23.0
650.0 | 21. 5,
675.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
650.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
650.0 1372.0
650.0 1372.0
ESD'3 TRIPS
650.0
650.0
1372.0
1372.0
12/0112005 14:58:41
TRI P S T AT US
R ES ET S
ES D 2
ES D 3
ES D 4
| 650.0 | 1372.0
Note: The resets refer only to Trip "Causes"and not "effects"
If a one of the trips is active, the effects of that and all subsequent trips are activated.
Figure A4.1.25: ICFBMR pilot plant control screen #5
118" chamf er o n
each co rner
3" x 3/8" sheet
(typ' 5) equally
spaced
{ 3/8" * |
4 x 'A" OD rings
o n bo x centreline
4 x 1/8" thick tab
1/8" ho le,
o n bo x centrelines
Connec ti on T a b s
Al l dimensions in inches
Al l materials carbon steel
Figure A4.1.26: I CF B MR dummy internals for commissioning
231
200
0 50 100 150 200 250 300
Nitrogen flow (SLM)
Figure A4.1.27 ICFBMR off-gas filter pressure drop
(Pure N
2
flow to reactor, 20C, ambient pressure downstream of filter, no catalyst in reactor)
Table A4.1.5: Natural gas analysis
Sample Location: BC Gas, Tilbury Gate Station, Delta BC (2002)
Analyzer: On-line Daniel gas chromatograph
Component Mole Percent (Volume Percent)
Nitrogen 0.7
Carbon Dioxide , 0 . 2
Methane 95.5
Ethane 2.9
Propane 0.5
iso-Butane 0.05
n-Butane 0.1
Pentanes 0.04
Hexanes 0.01
Total 100.00
Gross Heating Value (MJ/m
3
) 38.60 @ 15.0C and 101.325 kPa
Relative Density 0.580 @ 15.0C and 101.325 kPa
Average Molecular Weight 16.78
*Total Sulphur (mg S/m
3
) Approx. 15 (11 ppm)
Hydrogen Sulphide (mg/m
3
) Approx. 2 (1.5 ppm)
Water Content (mg/m
3
) Approx. 30 (40 ppm)
*Note: The total sulphur includes naturally occurring sulphur compounds plus added odorant
(approx. 5 mg S/m
3
or 3.5 ppm) plus hydrogen sulphide.
232
Appendix 4.2 - ICFBMR Assembly Procedure
1. General Notes
It is important that appropriate safety gear be worn during assembly. As a minimum, steel-toed boots,
eye protection, hardhat, work gloves and work clothes should be worn. Dust masks must be worn
when using insulation and other dusty materials.
Kaowool and ceramic blanket and paper insulation were used to insulate the inside of the carbon steel
outer reactor. Installers should be aware that the paper insulation has organic binders that release
vapour on heat-up. Care should be taken to bake these binders before closing up the reactor as the oils
can accumulate, leading to heater failure and condensation in vent tubing. All flange bolts should be
tightened in the appropriate "star"pattern.
2. Reactor to Horizontal
For the following instructions, it assumed that the reactor cradle swings north-south and that the
reactor is lowered due south.
Two people are required to lower the ICFBMR reactor to the horizontal position safely.
The main reactor support frame must be anchored to the ground to prevent movement. This can
be achieved by drilling screwed Hilti anchors into the cement floor. For the Gas Gun installation,
the reactor must be moved away from its location adjacent to the pilot plant, as there is
insufficient overhead and horizontal clearance.
Two block and tackles (or high quality chain pullers) are required to lower and raise the reactor.
See Figure A4.2.1. The reactor is balanced on the main support frame on the four horizontal
pipes. In order to lower, the reactor must first be pulled off vertical (Tackle #1) before the weight
is supported by the lowering tackle (Tackle #2).
Tackle #1: This is used to pull the reactor off vertical. Attach the fixed end of a block and tackle
(min 5 tonne capacity) to the horizontal bar opposite the side the reactor is being dropped. An
appropriately rated chain or lifting strap can be used. The hook of the tackle is then attached to
the eyebolt on the main lower flange at the due south position. Make sure that the tackle does not
bind when raised or lowered. Exert slight tension.
Tackle #2: This supports the weight of the reactor once it is pulled off vertical. Attach the fixed
end of a block and tackle (min 5 tonne capacity) to the horizontal bar side on which the reactor is
being lowered. An appropriately rated chain or lifting strap can be used. The hook of the tackle is
233
then attached to the lowest eyebolt located on the preheater wye pipe support guide. Make sure
that the tackle does not bind when raised or lowered. Apply slight tension.
Remove the two northern U-clamps that hold the main column supports. Loosen (do not remove!)
the two southern U-clamps so that the supports can pivot.
Put an operator on each tackle. Make sure that there is a clear escape route for each operator if
needed.
Slowly pull the reactor the reactor off vertical with Tackle #1. Tackle #2 MUST be tightened at
the same time to ensure that there is no slack.
At about 5, the reactor will be teeter as the weight shifts onto Tackle #2. Lower the reactor
slowly with Tackle #2. Take in the slack with Tackle #1.
A wheeled support leg is strapped to the upper reactor. Keep lowering the reactor onto the
support leg and then install the two horizontal guides to anchor the support leg to the main frame.
3. Main Flange Removal
Top flange (weight 145 kg): Attach a moveable crane to the flange eyebolt. Be careful to protect
the top flange gasket surface.
Remove the bottom flat flange (weight 145 kg). Attach a moveable crane to the flange eyebolt
with a tie rope to the bottom of the flange to prevent the flange from swinging out when it is
unbolted. Be careful to protect the top flange gasket surface.
Remove the preheater support section (wye) with an appropriately sized crane. The wye weighs
185 kg when empty, about 250 kg if the preheater is installed. Make sure the reactor is anchored
when removing to prevent the reactor shifting.
The reactor anchors can now be removed and the reactor assembly wheeled to the desired
location.
4. Internal Preheater Assembly (HI)
The preheater assembly consists of three separate stainless steel coils (two 3/8" tubes, one V" tube)
embedded into a cast lead block shaped into an annular block. One of the coils melted during the
block pour, so a separate coil for the oxidant supply was inserted tightly inside the preheater core.
The procedure below was used for the preheater assembly, but should not have to be repeated unless
there is a failure of some of the components. Figure A4.2.2 is a photograph of the complete preheater
assembly ready to be attached to the main reactor wye.
234
Place the two hemi-spherical Watl ow ceramic heaters adjacent to the pre-heater block. Attac h to
the block with metal strapping on the ceramic shoulders.
Attac h pigtail tubing to upstream end of pre-heater block. The tubing should have several corners
between the wy e end-cap and preheater to al l ow for thermal expansion between these two fixed
points.
Support wye end cap in the vertical position.
Install blanket insulation into bottom of wye end cap and around heaters.
Place the preheater b loc k assembly into wye piece end cap and rest onto the end support tabs. The
three tube ends should protrude through the wy e end. Bol t preheater in.
Place heater leads next to the wye shell and bring out lead ends through the main flange
connection. Insulate between heaters and the vessel. .
F rom outside, slip N P T tube fittings over preheater inlets and tighten to shell. Put tube fitting and
ferrules over tubes and tighten to seal. Teflon ferrules may be used to make the system
removable.
Li ft and bolt the wy e assembly to the main reactor flange
5. Main Column Insulation Liner and Power Lead Pass-Throughs
T wo insulated stainless sheaths are installed in the 16" (0.41 m) diameter c olumn. The following
procedure outlines how the sheaths and power leads were installed. Barri ng a failure, this should not
need to be repeated.
Drop the big wy e assembly.
Wrap and tape the two 13" (0.33 m) diameter stainless steel liners separately with blanket / paper
insulation until diameter of the 16" (0.41 m) c olumn is achieved.
Insert the longer liner from the bottom flange top until the top is about 23" (0.58 m) from the top
flange. The two lower nozzles (B and C) should be accessible from the inside.
There are six 240 V A C heater elements installed, each with two leads. The leads are brought through
three N P T - Conax fittings on Nozzl e B . Eac h fitting holds four insulated wire leads.
Place additional insulation, for example Teflon tubing, on the Conax leads that wi l l be inside the
reactor.
Make sure each end of the pass-through lead is labelled and then install the three N P T - Conax
fittings on the flange.
The 12 leads from the Conax fitting should be secured to the vessel wal l with aluminium tape and
directed towards the bottom open flange (M2).
235
There are a number of pass-through thermocouples on Nozzle C:
Place additional insulation, for example Teflon tubing, on the thermocouple leads inside the
reactor.
Make sure each end of the thermocouple is labelled and then install the Conax thermocouple
fittings on nozzle C.
The thermocouples should be secured to the vessel wall with aluminium tape and the wire sent
towards the bottom open flange (M2).
The shorter insulated stainless sheath is now installed in the 16" (0.41 m) column:
Insert the shorter insulated liner from the bottom flange top until it mates the upper liner
Take care that the power and thermocouple leads remain in place against the column wall
The thermocouple for the preheater block can now be placed (TE-110) into the drilled hole in the
end of the cast block
Raise and install the wye.
6. Internal Reactor Assembly
The internal reactor is made from 304 / 310 stainless steel. The system is designed for the main body
of the reactor to remain in the outer reactor, while internals are changed after removal via the top
flange.
Position the four Watlow tubular heaters on the internal reactor. Try to have the heater terminals
insulated and as far away as possible from the reactor. Attach the heaters with stainless steel
strapping. Figure A4. 2. 4 is a photograph of the four heaters strapped to the reactor, prior to
insulation wrapping.
Place the reactor wall thermocouple into the well (TE-108 top, TE-109 bottom). Bring the
thermocouple leads down past the bottom flange.
Attach the high temperature N i power leads to the heater terminals. Ensure that the terminals are
well insulated.
Insulate top of the heaters and upper reactor with ceramic paper and blanket until the diameter of
the insulation is about 12!4" (0.32 m) so as to slip into the stainless liner already installed in the
pressure vessel. Ensure that the heater and thermocouple leads are outside the insulation and are
taped down with aluminium tape. The heater leads are brought to the bottom of the assembly.
Screw in the stainless threaded rod supports into the 4 tabs on top of the internal reactor. The rods
should project about 19" (0.48 m) above the inner reactor flange.
236
With the top and bottom flanges off, insert the J-shaped lifting jig into the internal reactor from
the top. Lift the reactor with the jig with a crane.
Before inserting the reactor, place a 10' (3 m) long 3/8"(9.5 mm) OD tube in the sheath. This
will become line transferring oxidant gas from the preheater to the top of the internal reactor.
Insert the internal vessel into the pressure vessel via the top flange. If the insulation is tight, it
may be worthwhile to attach a rope or cable puller to the bottom flange to help insert the reactor.
Take care not to rip or detach the heater and thermocouple leads.
Take care not to rip the insulation on the inner reactor on the internal pressure vessel tabs. The
internal reactor has to be twisted slightly several times to allow the top flange to pass the tabs on
the pressure vessel.
Insert the internal reactor until it meets the top of the stainless sheath. Secure the four support
rods onto the internal taps with nuts.
When the distributor assembly is ready to be installed, place the gasket and bottom flange via the
bottom manway (M2). Use anti-seize on the bottom bolts. The flange bolt heads have been
shaved to lock on the backside of the flange when pulled, but might require a little playing while
bolting.
7. Heater Connections
All heater and power leads are now in the bottom wye. Connect the appropriate heater leads with
the Conax leads with heavy-duty connectors. Insulate the connections well and secure the wire
assemblies to the uninsulated shell of the wye.
Drill out the back of the electrical box to match the positions of the three Conax lead fittings on
nozzle B. Mount box to nozzle
Attach Conax leads to the appropriate slot on the terminal strip.
Check the resistances of each heater set. Check resistance to ground and the other heaters.
Connect the two reactor wall thermocouples (TE-108, TE-109) to the Conax plugs from nozzle
C.
8. Preheater Connections
The three outlets from the preheater are connected to the distributors. Remember to use anti-seize on
all tubing connections.
Connect the appropriate thermocouple into a tubing tee to measure the preheat temperature (TE-
111 main feed, TE-112 secondary feed, TE-113 oxidant).
Make sure that the connections have a couple of bends to allow for thermal expansion.
237
Pressure test and insulate lines.
9. Insertion of Reactor Internals
Insertion of the reactor internals can be tricky due the space constraints in the vessel headspace.
As many connections should be made as possible before inserting the internals.
Place the top inner gasket, and insert the reactor internals. Make sure the orientation is correct.
(See Figure A4. 2. 3).
Place and tighten top flange of the inner reactor.
The large diameter tubing in the top headspace should be tackled first:
Rel i ef / pressure line from the internal reactor (3/8", 9.5 mm) out through nozzle D
Reactor outlet from internal reactor filters (3/8", 9.5 mm) out through nozzle D
Rel i ef line from the external reactor (1", 25 mm): cap with screen to prevent plugging and bring
out through nozzle D
Filter backflush connections, i f required QA", 6 mm through nozzle D )
The reactor internals may consist of the following and are connected through the inner reactor top
flange:
Oxidant distributor: Connect to the preheat tube extending up the internal cladding.
Membrane panels wi th inlet (1/8", 3 mm) and outlet (Vi ", 6 mm). Connect with mating tubing
brought through nozzles E and D .
Pressure taps: Most easily brought out by the 1/8" (6 mm) Conax fittings. The taps are then
connected in the head space with 1/8" (6 mm) tubes
Thermocouples (1/8", 6 mm): Multipoint thermocouples are passed through the Conax split
fitting on nozzle G . Assemble fitting once all thermocouples are in place.
Final button-up:
Insulate branch nozzles once al l of the connections are made.
Pressure test the internal reactor and fittings. Chec k top and bottom connections.
10. Raise Reactor
I f not already done, the reactor needs to be raised to the vertical. This is done in the reverse order of
how it is lowered (described previously, see Figure A4. 2. 5). I f no overhead crane is available, it may
be preferable to attach the top flange ( M l ) before lifting. It can be swung open again once vertical.
238
The reactor can now be rolled to its final location and the four corners of the support structure
anchored. The internal reactor needs to be level, note that this may not be the same as levelling the
external vessel. Use shims under the main supports or the jackscrews. The main reactor and frame
needs to be connected to ground.
Once catalyst is filled, the top and bottom headspaces can be insulated and the top (Ml) and bottom
(M2) flanges placed. Pressure test the external vessel prior to operation.
11. Final External Connections
Make sure the 240VAC heater controllers are locked out. Attach the 240VAC leads and grounds
to the heater terminal box.
Connect three feed lines to preheater.
Connect nitrogen purge to preheater wye cap.
Plug in all thermocouples to the PLC
Connect pressure taps to transmitters and purge meters
Connect membrane sweep and permeate lines
Connect ROG (non-permeate reactor off-gas) outlet
Connect rupture disks and pipe to outdoors
If required, connect filter backslash piping.
Figure A4.2.1: ICFBMR block positions - Tackle #1 is right (north), Tackle # 2 is left (south)
239
Figure A4. 2. 2: ICFBMR preheater (HI) - note the three exit connections and heater leads
Figure A4.2.4: ICFBMR internal reactor shell and heaters (H2 and H3)
Appendix 4.3 - ICFBMR Operating Procedures
Pre-Operation
1 Gas chromatography (GC)
a. Ensure gas GC is on and calibrated.
b. Run gas standard.
2 Start P L C and control system:
a. Turn on 120 V A C power switch in heater control cabinet. The P L C indication lights
should go on.
b. Turn on 120 V A C power switch to solenoids in heater control cabinet.
c. Turn on 24 V D C breaker in P L C cabinet. Green light should go on the 24 V D C
power supply.
d. Turn on 120 V A C breaker in P L C cabinet to power the solenoids (push red button).
e. Power up the Human Machine Interface (HMI) computer.
f. Start HMI I CF B MR control program by clicking "Pilot Plant- I CF MB R " icon.
g. Check that inputs and outputs are connected on working.
h. If desired, shutdown and restart P L C data logger.
3 Ensure all cylinders in the outside shed are full and connected.
4 Ensure that fuel lines (hydrogen and methane) are purged to expel any oxygen.
5 Open flow of cooling water to the condenser E2 and check drain to confirm the flow.
6 Line up permeate:
a. Ensure that all permeate outlet valves are fully open.
b. Close all sweep rotameter valves.
c. Close all sweep inlet valves.
d. Ensure combined permeate line is vented.
7 Open nitrogen supply and adjust regulators:
a. Process (200 psig).
b. Purge (200 psig).
c. Sweep (20 psig).
8 F i l l water tanks:
a. Open vent solenoid valve of desired tank and throttle flow with manual valve.
b. When pressure is vented, open manual and solenoid water supply valves.
c. Monitor HMI and close water supply solenoid valve when tank is full.
d. Close vent valves.
242
9 Check level in E2 - should be small heel of water present for condensation of ROG.
10 Ensure that reactor off-gas (ROG) pressure control valve is fully open in manual (PCV-
272) and that valve bypass is open. Route ROG to vent.
11 External preheater:
a. Ensure preheater output is turned off in PLC.
b. Hook 120VAC power to the preheater magnetic switch in electrical cabinet and
energize switch.
c. Turn on 220 VAC preheater power supply in electrical cabinet.
12 ICFBMR heaters:
a. Ensure the ICFBMR heater controllers are in manual at 0%.
b. Ensure the supply switches to the three heaters are off on the ICFBMR heater control
box.
c. With the 480 VAC supply isolated, measure the resistance of the six ICFBMR
heaters at the supply box. (HI ~ 14 Q., H2 and H3 ~ 12 Q.).
d. Measure the resistance to ground for each heater set. It should ideally be greater than
0.2 MQ.
e. Turn on the 480 VAC supply to the transformer. Supply light should illuminate on
the transformer switch box.
f. Turn on the 240 - 480 VAC transformer via the transformer switch box. Power
supply should be indicated on the transformer switch box and the ICFBMR heater
control box.
Operation Start-up
1 Purge nitrogen:
a. Open flow to purge meters.
b. Slowly pressurize the external preheater to 75 psig (520 kPag) with the vent valve
closed.
c. Pressurize the two water tanks using manual and solenoid valves.
d. Make sure that the manual vent from the external ICFBMR vessel is closed.
e. Open nitrogen to the external ICFBMR pressure regulator, which should maintain the
pressure in the vessel at about 15 psig (100 kPag) over the internal reactor pressure.
2 Introduce process nitrogen:
a. Ensure that secondary feed line is lined up to branch from main feed line.
b. Ensure process nitrogen 3-way valve is routed to main feed line.
24 3
c. Ramp process nitrogen flow to 15- 20 S L M .
d. Open nitrogen supply to oxidant flowmeter and maintain small flow through the
oxidant distributor.
Purge permeate lines:
a. Open all sweep isolation valves to membranes.
b. Crack open sweep rotameters to trickle nitrogen through the membranes. It is
important to keep the permeate pressure very low to prevent reverse pressure on the
membranes.
Start heat-up:
a. Turn on external preheater control to 300C.
b. Turn on I CF B MR heater power supply (HI , H2 and H3) and put on low fire (5-15%).
c. Heat up the reactor at a rate of <2C/min, paying special attention to the core
membrane temperatures.
F i l l natural gas tanks:
a. Check pressure of the two natural gas tanks. The first tank (fill tank) should be at
about 2,000 psig and the second (feed tank) at about 1,000 psig.
b. If not to pressure, fill each tank to the desired pressure with the natural gas
compressor:
i . Open inlet valves to compressor.
i i . Line up compressor discharge to correct cylinder.
i i i . Start compressor and fill to desired pressure.
iv. Stop compressor and isolate tank and compressor.
c. Depending on the gas usage, the gas cylinders wi l l need periodic filling while
running. The Fuelmaker compressor has a capacity of about 53 S L M .
Introduce hydrogen:
a. Open the hydrogen supply and set regulator at 200 psig (1,400 kPag).
b. Open the hydrogen supply solenoid.
c. Once the core reactor has stabilised at 250C, gradually introduce hydrogen up to a
composition of 15-20% hydrogen. Process nitrogen can be cut back as the reactor
heats up to conserve supplies.
Raise temperature:
a. Heat the reactor at a rate of <3C/min, paying special attention to the core membrane
temperatures.
24 4
b. Once the core has reached about 500C, increase the reactor pressure to about 30
psig (200 kPag). Watch the external I CF B MR pressure to see if it follows
automatically. I f it does not, investigate the operation of the tracking regulator.
8 Introduce steam:
a. Check the R OG temperature exit El , which wi l l likely start to show increased
temperature.
b. Ensure water control valve is closed.
c. Open water feed manual / automatic valves on one of the tanks.
d. Crack open the water control valve to feed water at a low rate (2-3 kg/h).
e. Monitor the feed line temperatures and pressures to ensure that the feed to the reactor
is fully vaporized.
f. Supply steam for 30 minutes and check R OG composition for any carbon reduction.
9 Introduce methane:
a. Line up the second (fill tank) gas cylinder (fill tank at 500 (3,450 kPag) to 1,000
(6,900 kPag) psig) and isolate the connection between the two cylinders.
b. Set the gas regulator in the cylinder shed at 200 psig (1,400 kPag)
c. Open the methane supply valve in the cylinder shed.
d. Open the methane isolation valve upstream of the gas controller.
e. Open the methane supply solenoid via the HMI .
f. Crack the methane flow and gradually increase to match desired steam-to-carbon
ratio.
10 Stabilize operations:
a. Maintain temperature uniformity in bed by adjusting heater settings.
b. Take samples of the ROG using the direct sample line to GC#1. Once CO or C0
2
shows up in the ROG to confirm reaction, the hydrogen supply can be closed:
i . Shut hydrogen controller via the HMI .
i i . Close hydrogen supply solenoid via the HMI .
i i i . Close isolation valve in cylinder shed and isolate hydrogen cylinders.
c. Take GC analyses of the ROG until reproducible values are achieved.
d. Watch the I CF B MR pressure and stabilise operations.
e. Sweep nitrogen flows can be gradually increased, but always ensure that the
permeate pressure is well below the reactor pressure.
245
Shutoff heaters (4):
a. Turn off the three ICFBMR heaters on the HMI.
b. Shut the three ICFBMR heaters switches on the control box.
c. Turn off ICFBMR transformer and 480 VAC supply.
d. Turn off external process heater on HMI.
e. Turn off 120 VAC supply to external preheater magnetic switch.
f. Turn off 240 VAC supply to external preheater.
Reduce NG and steam flows in tandem to a minimum value. The endothermic reforming
reaction can be used to help reduce the reactor temperature.
Introduce hydrogen to the feed with the H2 mass flow controller.
Reduce pressure:
a. Slowly reduce the reactor pressure to 30 - 45 psig (200 - 300 kPag). This can be
done in conjunction with feed flow reduction.
b. As preheater feed pressure drops, manually vent pressure from external preheater
shell while reducing nitrogen padding regulator.
c. TR-123, the ICFBMR tracking regulator, should vent pressure in the outer ICFBMR
vessel to follow the internal pressure, but this has been known not to work. Watch the
pressure balance and manually vent pressure if necessary. Note that the rupture disk
between the two ICFBMR vessels is designed to relieve at 100 psi (690 kPa)
differential pressure.
Reduce sweep nitrogen flows to minimum value to conserve nitrogen.
Shutoff NG and steam:
a. Open process nitrogen to about 10 SLM (ensure it is connected to the main feed line)
and adjust hydrogen flow to give desired concentration.
b. Shut NG flow via controller:
1. Shut NG feed solenoid via the HMI.
2. Close manual valve just upstream of the NG controller.
3. Close NG delivery valve in the cylinder shed.
4. If not done already, stop gas compressor and isolate suction and discharge.
5. Close and isolate NG delivery tanks.
c. Stop steam flow several minutes after NG:
1. Close water feed throttling valves.
2. Close manual and solenoid valve on feed delivery from water tanks.
24 6
3. Close steam feed isolation valve.
4. I f shutting down for a lengthy period, isolate nitrogen pad from both water
tanks and vent pressure.
d. It is important that all steam be purged from the preheater and reactor. Maintain gas
flow for at least 2 hours after steam shutoff.
7 Once the reactor pressure has been reduced to less than 60 psig (400 kPag), fully open
the vent from the outer I CF B MR vessel and external preheater.
8 Reduce the reactor core temperature to 250C. Depending on the process flows this can
take many hours. It is important that a significant partial hydrogen of hydrogen is
maintained in the reactor during this time to prevent membrane damage. It is also
preferable to maintain a small positive pressure (15-30 psig, 100-200 kPag) to ensure that
the membrane is pressed onto its support.
9 Stop hydrogen once the membrane temperature has reached 250C:
a. Shutoff hydrogen flow controller via the HMI .
b. Close hydrogen supply solenoid valve via the HMI .
c. Close manual valve just upstream of the hydrogen controller.
d. Close hydrogen delivery valve in the cylinder shed and isolate cylinders.
10 Maintain process and purge hydrogen for several hours to purge hydrogen from the
membranes and reactor.
11 Stop sweep nitrogen:
a. Keep membrane outlets open.
b. Close membrane sweep inlets.
c. Isolate nitrogen sweep cylinders and feed valve in cylinder shed.
12 Shutoff process nitrogen:
a. Fully open R OG pressure valve (PCV-272) and open manual bypass.
b. Reduce and stop process nitrogen via HMI controller. Close process nitrogen supply
valve and isolate cylinders in shed.
13 Close purge nitrogen suply valve and isolate cylinders in shed.
14 Shutoff cooling water to E2.
247
Operation Running Checklist
Below is a list of operating tasks required to keep the pilot plant running. These tasks are in addition
to any experimental activities.
Table A4.3.1: Operator task checklist
Task Frequency
1 Check cylinder pressures, especially nitrogen:
Once new cylinder is on, check on post-
regulator pressure as small differences can make
differences, for example the water flow from the
tanks
Every 30 mins
2 Check for low levels in water tanks on computer and fill
when switching:
Make sure second tank is full, close vent
(manual and solenoid valve) and open nitrogen
pad (manual and solenoid valve)
Open discharge solenoid on second tank
Open manual discharge valve on the second tank
and at the same time close the discharge on the
first tank
Close water discharge solenoid valve on first
(empty) tank
Vent empty tank via manual and solenoid valves
When empty, open manual and solenoid water
fill valves
When HMI indicates as full, open manual and
solenoid water fill valves
Close vent on filled tank (manual and solenoid)
and open nitrogen pad. Tank is now ready to be
placed on-line
When low level alarm shows
on HMI
3 Drain E2 - do not drain fully empty as heel of water is
used for condensation. Take care of the hot water under
pressure.
Every time new water tank is
introduced
4 Check permeate line temperatures to ensure no large
leaks
Hourly
5 Check preheater shell pressure. Manually pad or vent if
necessary to maintain a shell overpressure of 15-45 psi
30 mins or more frequently
when changing reactor
pressure
6 Check external ICFBMR pressure and manually vent if
necessary
30 mins or more frequently
when changing reactor
pressure
248
Appendix4. 4 - Catalyst Microreactor System
A microreactor test stand owned by Membrane Reactor Technologies Ltd. was used to evaluate the
catalysts used in the ICFBMR pilot reactor. Rigorous catalyst testing was not undertaken; rather
simple, standard experiments were conducted to check the reactivity of catalyst samples before and
after pilot plant runs. Both the nickel-based SMR and noble metal ATR catalysts were tested.
Figure A4.4.1 presents a flow schematic of the microreactor. Mass flow controllers set the gas and
water flows. The feed was heated and water vaporized in an electrical preheater prior to being
introduced into the heated microreactor. The system could run unattended and was connected to a
supervisory computer, which logged data and performed safety shutdowns. Reactor exit gases were
analyzed in a gas chromatograph. Figure A4.4.2 presents details of the downflow microreactor.
Vent
GC
Figure A4.4.1: Microreactor flow schematic
249
F l o w i n
Watlow ceramic
cylindrical heater
(550W, 372" OD,
ID, 12"long)
Thermocouple
Thermocouple
(1/16"OD, moveable)
Thermocouple
sheath (1/8"OD)
Reactor tube
(3/8"OD, %"ID)
Ceramic microspheres
(1 mm diam)
Quartz wool
Catalyst sample
Alumina powder
Quartz wool
Ceramic microspheres
F l o w out
Figure A4. 4. 2: Microreactor geometry
250
Appendix 4.5 - Commissioning
Plan
-133-
u
VA" (6 mm) ring heater
Section
18
Single 0.6 mm orifice at each
of the 4 distribution points
VJ" (6 mm) feed line
Figure A4. 5. 1: Original pilot I CF B MR secondary distributor (dimensions in mm)
VA" (6 mm) SS tube
fitting for inlet
Heavy wall %"
(15 mm) SS pipe
14-1 mm diameter orifices
(7 per side)
Figure A4. 5. 2: Original pilot I CF B MR air distributor
251
4
2
y = 4.77E-04X
2
+ 2.67E-02x + 2.52E-01
R
2
= 0.9998
A
.
A
A "
0 10 20 30 40 50 60
Ro tameter Reading
Figure A4.5.3: Calibration of helium rotameter (CHE 4251C) at 1,380 kPag
252
Appendix 4.6 - ICFBMR Pilot Plant Data
Table A4. 6. 1: Gas chromatograph analyses from I CF B MR helium tracer testing (reactor at 1,100 kPa,
core at ~595C, natural gas feed = 42 S L M , steam-to-carbon ratio = 3.0, no air, N
2
content due
to purges to pressure impulse lines)
Sample lo catio n GC analysis (dry) CH4
co nversio n
Sample lo catio n
H2 N2 CO CH4 C02 He
CH4
co nversio n
Reacto r off-gas 45.76 7.29 0.89 29.84 15.61 0.610 35. 6%
Po int 1 (annulus) 45.01 20.75 6.53 10.36 17.06 0.295 69. 5%
Po int E (bottom slot 2) 51.66 10.10 3.11 21.41 13.69 0.030 4 4 . 0%
Po int D (top slot 2) 39.61 30.81 3.46 13.00 13.07 0.043 56. 0%
Po int H (top slot 3) 48.24 11.58 3.39 20.04 16.73 0.031 50. 1%
Table A4. 6. 2: Membrane flux testing during run #5
(Pure H2 feed to reactor, no sweep to permeate)
Reactor Permeate H2 feed to Measured Predicted fluxfor Effective Effective /
Reactor pressure pressure reactor H2 flux area = 0.0258 m2 permeation theoretical
Membrane Date Time temp. (C) (kPa a) (kPa a) (SLM) (SLM) (SLM) area (m2) area
#5 July 11 05 2023 555 206 101 19.1 1.91 2.70 0.0183 70.8%
All 6 July 11 05 2049 555 266 101 19.1 11.29 3.93 0.0742 47.9%
All 6 July 11 05 2053 555 250 101 19.1 10.59 3.62 0.0756 48.8%
#3 July 11 05 2103 555 250 101 19.1 1.81 3.62 0.0129 50.2%
#4 July 11 05 2102 555 250 101 19.1 1.38 3.62 0.0099 38.2%
#1 July 11 05 2109 555 250 101 19.1 2.02 3.62 0.0144 55.8%
#8 July 11 05 2114 555 250 101 19.1 1.74 3.62 0.0124 48.0%
#6 July 11 05 2115 555 250 101 19.1 1.12 3.62 0.0080 30.9%
#5 July 11 05 2119 555 250 101 19.1 2.47 3.62 0.0176 68.4%
All 6 July 11 05 2127 555 150 101 19.1 4.94 1.38 0.0924 59.7%
#3 July 11 05 2154 555 150 101 19.1 0.64 1.38 0.0119 46.2%
#4 July 11 05 2150 555 150 101 19.1 0.57 1.38 0.0106 41.2%
#1 July 11 05 2157 555 150 101 19.1 0.87 1.38 0.0163 63.3%
#8 July 11 05 2204 555 150 101 19.1 0.55 1.38 0.0103 39.8%
#6 July 11 05 2206 555 150 101 19.1 0.37 1.38 0.0070 27.1%
#5 July 11 05 2210 555 150 101 19.1 1.03 1.38 0.0193 74.7%
Membrane number #1 #3 #4 #5 #6 #8
Average 0.0154 0.0124 0.0102 0.0184 0.0075 0.0113
Standard deviation 0.0014 0.0007 0.0005 0.0008 0.0007 0.0015
253
Table A4. 6. 3: Membrane flux testing during run #6
(Pure H
2
feed to reactor, no sweep to permeate)
Membrane Date Time
Reactor
temp. ("C)
Reactor
pressure
(kPa a)
Permeate
pressure
(kPa a)
H2 feed to
reactor
(SLM)
Measured
H2 flux
(SLM)
Predicted flux for
area = 0.0258 m2
(SLM)
Effective
permeation
area (m2)
Effective /
theoretical
area
#4 Aug 18 05 1300 551 164 101 10.0 0.59 1.72 0.0089 34.6%
#4 1306 553 174 101 10.0 0.70 1.96 0.0092 35.6%
#3 1310 553 180 101 10.0 0.96 2.11 0.0117 45.4%
#3 1315 553 182 101 10.0 0.96 2.15 0.0115 44.5%
#1 1322 560 180 101 10.0 1.16 2.13 0.0141 54.7%
#1 1322 560 180 101 10.0 1.17 2.13 0.0141 54.8%
#8 1326 562 178 101 10.0 0.48 2.09 0.0059 22.9%
#8 1328 562 178 101 10.0 0.49 2.09 0.0061 23.6%
#8 1346 570 208 101 13.6 0.81 2.81 0.0075 28.9%
#8 1348 570 213 101 13.6 0.92 2.92 0.0082 31.7%
#8 1350 570 213 101 13.0 0.90 2.92 0.0079 30.7%
#6 1353 570 217 101 13.0 0.90 3.01 0.0077 29.8%
#6 1355 570 217 101 13.0 0.96 3.01 0.0083 32.0%
#5 1357 569 219 101 13.0 1.95 3.05 0.0165 64.0%
#5 1357 569 219 101 13.0 1.80 3.05 0.0152 58.9%
#3 1410 565 199 101 13.0 1.26 2.59 0.0125 48.5%
#3 1411 565- 199 101 13.0 1.31 2.59 0.0130 50.5%
#4 1416 565 201 101 13.0 1.05 2.63 0.0103 40.0%
#4 1417 567 201 101 13.0 1.01 2.64 0.0099 38.4%
#1 1419 565 201 101 13.0 1.52 2.63 0.0149 57.8%
#1 1420 567 201 101 13.0 1.54 2.64 0.0150 58.2%
#8 Aug 19 05 1219 576 204 101 12.0 0.67 2.75 0.0063 24.4%
#8 1??5 576 204 101 12.0 0.69 2.75 0.0065 25.2%
#6 1227 574 204 101 12.0 0.56 2.74 0.0052 20.3%
#6 1228 573 204 101 12.0 0.52 2.73 0.0049 19.0%
#5 1231 572 201 101 12.0 1.54 2.66 0.0149 57.8%
#5 1233 572 201 101 12.0 1.59 2.66 0.0154 59.8%
#3 1237 570 204 101 13.0 1.26 2.72 0.0120 46.4%
#3 1238 570 204 101 13.0 1.26 2.72 0.0120 46.4%
#4 1242 570 201 101 13.0 1.07 2.65 0.0104 40.3%
#4 1243 570 201 101 13.0 1.07 2.65 0.0104 40.3%
#1 1246 570 201 101 13.0 1.32 2.65 0.0128 49.7%
#1 1247 570 201 101 13.0 1.33 2.65 0.0130 50.2%
#6 repeat 1251 570 201 101 13.0 0.52 2.65 0.0051 19.6%
#6 1252 570 201 101 13.0 0.51 2.65 0.0050 19.4%
#8 Aug 20 05 1130 585 196 101 13.0 1.09 2.60 0.0108 41.8%
#8 1131 585 196 101 13.0 1.08 2.60 0.0107 41.6%
#8 1135 585 196 101 13.0 0.97 2.60 0.0097 37.5%
#6 1139 585 199 101 13.0 0.78 2.67 0.0076 29.4%
#6 1140 585 199 101 13.0 0.77 2.67 0.0075 29.0%
#5 1143 585 199 101 13.0 1.93 2.67 0.0187 72.4%
#5 1144 585 199 101 13.0 1.88 2.67 0.0182 70.6%
#3 1150 585 203 101 13.0 1.16 2.76 0.0108 41.9%
#3 1151 585 203 101 13.0 1.14 2.76 0.0107 41.4%
#4 1146 587 197 101 13.0 1.03 2.63 0.0101 39.3%
#4 1147 587 197 101 13.0 0.97 . 2.63 0.0096 37.1%
#1 1155 586 203 101 13.0 1.58 2.76 0.0148 57.2%
#1 1156 586 I 203 101 13.0 1.56 2.76 0.014E 56.3%
Membrane number #1 #3 #4 #5 #6 #8
Average 0.0142 0.0118 0.0099 0.0165 0.0064 0.0080
Standard deviation 0.0009 0.0008 0.0006 0.0016 0.0015 0.0019
254
Table A4. 6. 4: Summary of Selected I CF B MR Pilot Tests (Sheet 1)
# Run Date Time Catalyst Feed flow (SLM) Steam:
carbon
ratio
02: ROG (dry basis)
# Run Date
Type Activity NG H20 N2 Air
Steam:
carbon
ratio
carbon
ratio
H2 N2 CO CH4 C02 Flow
SLM
1 2 Aua 10/04 1951 NiO OK 41.97 109.7 3.9 0 2.61 0 37.024 5.322 0.282 46.590 10.783 72.80
2 2 Aug 10/04 2028 NiO OK 41.99 128.5 3.8 0 3.06 0 37.681 5.169 0.293 45.245 11.611 73.47
3 2 Aug 10/04 2209 NiO OK 35.79 141.1 11.7 0 3.94 0 26.831 19.479 0.000 49.958 9.733 59.96
4 2 Aug 10/04 2224 NiO OK 41.99 128.5 4.8 0 3.06 0 30.801 7.088 0.137 50.957 11.017 67.60
5 2 Aug 11/04 1518 NiO OK 42.22 134.8 9.2 0 3.19 0 39.923 10.723 0.430 36.698 12.227 85.54
6 2 Aug 11/04 1536 NiO OK 42.24 134.8 9.2 0 3.19 0 39.293 10.863 0.408 37.263 12.174 84.74
7 2 Aug 11/04 1956 NiO OK 42.22 128.5 7.3 0 3.04 0 30.216 10.241 0.261 48.013 11.270 70.91
8 2 Aug 11/04 2008 NiO OK 42.22 128.5 7.8 0 3.04 0 26.212 11.466 0.319 51.525 10.477 67.75
9 2 Aug 11/04 2148 NiO OK . 42.19 128.5 10.6 0 3.05 0 32.018 13.632 0.385 41.918 12.047 77.63
10 2 Aug 12/04 1619 NiO OK 42.12 122 14.4 70.4 2.90 0.35 22.947 48.115 0.253 17.442 11.243 145.55
11 2 Aug 12/04 1638 NiO OK 42.14 122 15.1 70.4 2.90 0.35 23.310 48.057 0.310 17.296 11.027 147.17
12 2 Aug 12/04 1952 NiO OK 42.12 125 13.5 70.4 2.97 0.35 18.157 50.854 0.130 20.211 10.649 135.92
13 2 Aug 12/04 2020 NiO OK 42.09 125 13.3 70.3 2.97 0.35 17.680 51.092 0.120 20.482 10.627 134.78
14 2 Aug 12/04 2145 NiO OK 42.07 122 14.3 70.2 2.90 0.35 16.780 51.914 0.070 20.811 10.427 134.38
15 2 Aug 12/04 2206 NiO OK 42.09 122 13.5 70.1 2.90 0.35 17.008 51.499 0.095 20.791 10.607 133.65
16 3 Sep 20/04 1548 NiO OK 15.0 45.1 1.7 0 3.0 0.0 46.271 5.327 0.500 34.033 13.869 31.05
17 3 Sep 20/04 1616 NiO OK 15.0 45.1 1.9 0 - 3.0 0.0 48.407 5.808 0.723 30.650 14.413 32.83
18 3 Sep 20/04 1740 NiO OK 15.0 45.1 2.3 0 3.0 0.0 46.042 7.049 0.909 30.363 15.637 32.04
19 3 Sep 20/04 1809 NiO OK 15.0 45.1 2.3 0 3.0 0.0 46.287 7.187 0.883 30.003 15.640 32.30
20 3 Sep 20/04 1841 NiO OK 15.0 45.1 2.4 0 3.0 0.0 46.044 7.336 0.893 30.019 15.708 32.24
21 3 Sep 20/04 1917 NiO OK 1S.0 45.1 2.3 0 3.0 0.0 47.217 7.061 0.888 29.648 15.187 32.87
22 3 Sep 20/04 2219 NiO OK 15.0 45.1 2.0 0 3.0 0.0 46.999 6.318 0.912 29.662 16.109 32.20
23 3 Sep 21/04 1338 NiO OK 15.0 58.5 3.3 0 3.8 0.0 35.523 11.582 0.412 34.627 17.857 28.41
24 3 Sep 21/04 1430 NiO OK 15.0 35.5 6.2 0 2.4 0.0 30.744 20.317 0.384 30.263 18.292 30.71
25 3 Sep 21/04 1450 NiO OK 15.0 31.9 6.6 0 2.1 0.0 34.289 20.131 0.366 26.989 18.226 32.97
26 3 Sep 21/04 1545 NiO OK 15.0 47.3 5.2 0 3.1 0.0 41.349 15.040 0.499 22.552 20.561 34.46
27 3 Sep 21/04 1645 NiO OK 15.0 50.8 5.3 0 3.4 0.0 40.297 15.581 0.550 25.974 17.598 34.06
28 3 Sep 21/04 1734 NiO OK 15.0 60.1 7.9 0 4.0 0.0 39.598 20.881 0.496 22.049 16.976 38.03
29 3 Sep 21/04 1805 NiO OK 15.0 33.1 8.5 0 22 0.0 34.327 23.690 0.608 25.569 15.807 35.80
30 3 Sep 21/04 1905 NiO OK 15.0 45.1 7.0 0 3.0 0.0 39.270 19.236 0.506 24.257 16.731 36.22
31 3 Sep 21/04 2016 NiO OK 15.0 45.1 5.6 0 3.0 0.0 41.152 16.035 0.576 23.234 19.003 35.11
32 3 Sep 21/04 2054 NiO OK 20.0 60.1 8.5 0 3.0 0.0 39.520 18.027 0.412 27.136 14.905 47.18
33 3 Sep 22/04 1330 NiO OK 20.1 60.2 3.2 0.0 3.0 0.00 40.430 8.174 0.348 33.611 17.437 39.01
34 3 Sep 22/04 1423 NiO OK 20.1 60.2 3.5 11.4 3.0 0.12 32.433 26.014 0.384 25.392 15.774 48.26
35 3 Sep 22/04 1450 NiO OK 20.1 60.2 5.6 22.9 3.0 0.24 25.376 40.426 0.220 19.297 14.681 58.63
36 3 Sep 22/04 1550 NiO OK 20.1 602 6.7 33.9 3.0 0.36 23.105 48.120 0.216 14.571 13.987 69.68
37 3 Sep 22/04 1642 NiO OK 20.1 602 6.9 45.6 3.0 0.48 20715 54.028 0.167 11.445 13.646 79.38
38 3 Sep 22/04 1741 NiO OK 20.1 60.2 7.3 45.6 3.0 0.48 21.765 53.466 0.160 11.144 13.466 80.95
39 3 Sep 22/04 1807 NiO OK 20.1 60.2 7.9 58.2 3.0 0.61 19.132 58.932 0.163 8.395 13.379 91.40
40 3 Sep 22/04 1848 NiO OK 20.1 60.2 7.6 58.2 3.0 0.61 19.471 58.609 0.166 8.445 13.308 91.47
41 4 Oct 26/04 1600 NiO OK 30 90 5.4 0 3.0 0.0 37.214 9.529 0.459 39.706 13.093 56.33
42 4 Oct 26/04 2043 NiO OK 30 90 3.7 0 3.0 0.0 37.132 6.832 0.660 40.286 15.090 53.54
43 4 Oct 26/04 850 NiO OK 30 90 5.2 0 3.0 0.0 32.246 9.996 0.4888 44.186 13.084 51.94
44 4 Oct 26/04 916 NiO OK 30 90 4.3 0 3.0 0.0 32.185 8.5022 0.4789 45.608 13.226 50.58
45 4 Oct 26/04 2155 NiO OK 30 114 11.0 0 3.8 0.0 24.256 20.319 3.191 38.198 14.036 54.13
46 4 Oct 27/04 1018 NiO OK 30 114 3.6 0 3.8 0.0 38.908 6.5729 0.4161 40.634 13.469 55.03
47 4 Oct 27/04 1054 NiO OK 30 114 3.6 0 3.8 0.0 38.083 6.6012 0.4086 40.99 13.917 54.23
48 4 Oct 27/04 521 NiO OK 30 66 6.2 0 2.2 0.0 27.949 12.36 0.5435 45.645 13.503 50.26
49 4 Oct 27/04 618 NiO OK 30 66 5.8 0 2.2 0.0 23.613 12.376 0.4649 50.138 13.408 46.87
50 4 Oct 27/04 716 NiO OK 30 66 5.1 0 2.2 0.0 26.642 10.712 0.5099 49.853 12.283 47.89
51 4 Oct 27/04 745 NiO OK 30 66 4.6 0 2.2 0.0 26.804 9.7475 0.5046 50.611 12.333 47.26
52 4 Oct 27/04 1553 NiO uncertain 20 60 4.2 0 3.0 0.0 37.356 10.953 0.9318 33.303 17.456 38.69
53 4 Oct 27/04 2041 NiO uncertain 30 114 4.9 0 3.8 0.0 45.123 7.7139 1.08 29.648 16.436 63.61
54 4 Oct 27/04 2103 NiO uncertain 30 114 5.5 0 3.8 0.0 44.531 8.5386 1.0883 29.464 16.378 63.92
55 4 Oct 27/04 2213 NiO uncertain 30 66 5.8 0 2.2 0.0 31.026 11.161 1.1048 42.614 14.095 51.89
56 4 Oct 27/04 2252 NiO uncertain 30 66 5.8 0 2.2 0.0 31.732 11.06 1.0399 41.678 14.491 52.44
57 4 Oct 28/04 50 NiO uncertain 30 114 5.0 0 3.8 0.0 43.372 8.0838 1.0349 30.248 17.261 61.80
58 4 Oct 28/04 124 NiO uncertain 30 114 5.3 0 3.8 0.0 43.077 8.5152 1.0154 30.275 17.118 61.97
59 4 Oct 28/04 335 NiO uncertain 30 114 5.9 0 3.8 0.0 41.172 9.6645 1.2132 33.386 14.565 61.02
60 4 Oct 28/04 403 NiO uncertain 30 114 5.8 0 3.8 0.0 40.839 9.5992 1.1945 33.856 14.512 60.53
61 4 Oct 28/04 500 NiO uncertain 30 114 5.1 0 3.8 0.0 39.12 8.8884 1.2827 34.897 15.812 57.70
62 4 Oct 28/04 531 NiO uncertain 30 114 5.0 0 3.8 0.0 40.592 8.4913 1.2083 33.88 15.828 58.92
63 6 Aug 18705 ATR OK 20.0 60 1.0 0 3.0 0.0 37.942 2.839 0.649 44.455 14.116 33.77
64 6 Aug 18/05 ATR OK 20.0 60 1.0 0 3.0 0.0 41.199 2.696 0.762 40.233 15.111 35.65
65 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 42.982 2.497 0.855 38.256 15.411 36.68
66 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 41.870 2.591 0.884 37.545 17.111 36.01
6? 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 41.860 2.540 0.899 37.405 17.297 35.97
66 6 Aug 18/05 ATR OK 20.0 60 1.5 0 3.0 0.0 34.524 4.460 0.596 46.147 14.275 32.78
6S 6 Aug 18/05 ATR OK 20.0 60 1.5 0 3.0 0.0 35.639 4.460 0.584 45.345 13.972 33.39
7C 6 Aug 18/05 ATR OK 20.0 60 1.4 0 3.0 0.0 38.052 4.104 0.574 41.301 15.969 34.58
71 6 Aug 19/05 ATR maybe low 20.0 76 1.2 0 3.8 0.0 40.702 3.316 0.294 42.796 12.892 35.73
7; 6 Aug 19/05 ATR maybe low 20.0 76 1.2 0 3.8 0.0 41.623 3.328 0.311 42.123 12.615 36.33
7: 6 Aug 19/05 ATR maybe low 20.0 76 1.3 0 3.8 0.0 38.751 3.701 0.322 43.127 14.099 34.75
T 6 Aug 19/05 ATR low 20.0 44 1.7 0 2.2 0.0 32.186 5.365 0.231 51.621 10.596 32.03
71 > 6 Aug 19/05 ATR low 20.0 44 1.6 0 2.2 0.0 30.581 5.270 0.291 53.071 10.788 31.18
7( > 6 Aug 19/05 ATR low 20.0 44 1.7 0 2.2 0.0 31.756 5.409 0.304 49.445 13.085 31.83
7
-
' 6 Aug 19/05 ATR low 20.0 | 44 1.7 0 2.2 0.0 29.042 5.686 0.287 52.081 12.905 30.64
255
Table A4.6.4: Summary of Selected ICFBMR Pilot Tests (Sheet 2)
# CH4 conversion Steam InROG [H21wet in ROG Core Pressure (kPa)
Measured Equilibrium from ROG GC from GC predicted by equil temp Reactor Permeate
ROG *lo H2 perm H2 perm SLM [H20] w/ H2 flux no H2 flux (C)
1 19.2% 20.9% 23.5% 93.8 56.30 23.7% 19.2% 19.9% 506 702 101
2 20.8% 21.5% 24.2% 111.2 60.22 23.5% 17.8% 18.5% 496 713 101
3 16.3% 22.4% 25.6% 129.4 68.34 15.9% 14.9% 15.5% 499 1100 101
4 18.0% 18.5% 21.2% 113.5 62.67 18.9% 15.4% 16.1% 499 1124 101
5 25.6% 26.4% 29.5% 113.5 57.03 25.4% 20.2% 20.9% 522 745 101
6 25.2% 25.9% 29.0% 113.8 57.32 25.0% 19.8% 20.6% 519 742 101
7 19.4% 23.1% 26.8% 112.3 61.30 18.7% 18.4% 19.3% 530 1120 101
8 17.3% 23.8% 27.5% 114.1 62.74 16.1% 18.9% 19.8% 533 1096 101
9 22.9% 25.8% 30.1% 109.5 58.52 20.2% 19.8% 20.9% 547 1145 101
10 39.7% 46.9% 49.9% 88.9 37.92 16.6% 21.5% 22.2% 534 662 101
11 39.6% 45.6% 48.6% 89.1 37.71 16.9% 20.6% 21.4% 534 746 101
12 34.8% 41.8% 46.3% 95.9 41.36 12.8% 17.8% 18.8% 534 1109 101
13 34.4% 41.5% 46.1% 96.2 41.65 12.5% 17.6% 18.6% 532 1107 101
14 33.5% 40.0% 44.4% 93.9 41.13 11.9% 16.8% 17.7% 535 1331 101
15 34.0% 40.2% 44.6% 93.5 41.17 12.0% 17.0% 18.0% 537 1328 101
16 29.7% 29.0% 42.9% 36.3 53.91 30.1% 20.6% 24.0% 553 881 101
17 33.1% 32.5% 46.5% 35.4 51.88 31.9% 22.6% 26.2% 574 931 101
16 35.3% 32.5% 48.8% 34.8 52.05 30.3% 21.9% 26.0% 590 1211 101
19 35.5% 32.3% 51.5% 34.7 51.79 30.5% 21.1% 25.9% 589 1214 101
20 35.6% 32.3% 52.3% 34.7 51.82 30.3% 0.209 0.259 589 1209 101
21 35.2% 32.5% 42.6% 34.8 51.43 31.2% 0.233 0.260 590 1213 101
22 36.5% 34.5% 52.9% 34.4 51.67 31.0% 0.226 0.274 591 1047 101
23 34.5% 32.4% 48.0% 48.2 62.92 21.8% 18.6% 21.9% 571.5 1427 101
24 38.2% 25.8% 40.5% 24.1 43.98 21.4% 19.3% 23.2% 569.4 1132 101
25 40.8% 26.3% 40.8% 19.8 37.52 24.9% 20.4% 24.6% 582.8 1149 101
26 48.3% 35.8% 51.6% 32.9 48.87 27.8% 22.3% 26.3% 596.9 1174 101
27 41.1% 35.2% 50.4% 38.6 53.15 26.3% 21.3% 24.9% 592.1 1288 101
28 44.2% 41.9% 53.9% 47.0 55.28 25.5% 22.5% 25.3% 596.4 1165 101
29 39.1% 28.4% 41.1% 21.5 37.56 25.0% 21.3% 25.0% 596.9 1274 101
30 41.5% 33.3% 43.1% 32.8 47.51 26.6% 22.4% 24.9% 588.1 1174 101
31 45.7% 32.6% 47.4% 31.5 47.33 27.9% 21.3% 25.0% 581.3 1089 101
32 36.1% 29.9% 37.9% 45.8 49.27 26.5% 21.0% 23.0% 566.9 1101 101
33 34.6% 27.9% 36.6% 46.4 54.33 26.2% 20.8% 23.0% 558.5 1081 101
34 38.9% 33.3% 42.5% 44.7 48.11 21.9% 19.9% 22.0% 556.25 1137 101
35 43.6% 39.5% 48.3% 42.8 42.20 17.8% 19.2% 21.2% 556.5 1186 101
36 49.4% 46.4% 55.5% 40.5 36.76 16.9% 19.3% 21.3% 555.5 1082 101
37 54.7% 52.2% 60.6% 38.4 32.58 15.6% 19.0% 20.8% 556 1135 101
38 55.0% 52.0% 61.0% 38.2 32.07 16.5% 18.6% 20.6% 553.25 1110 101
39 61.7% 59.9% 68.5% 35.5 28.00 14.9% 19.1% 21.0% 560.75 1132 101
40 61.5% 59.9% 68.7% 35.7 28.05 15.2% 19.1% 21.1% 561 1133 101
41 25.4% 32.2% 37.4% 75.0 57.11 23.7% 24.3% 25.8% 570 901 101
42 28.1% 32.1% 38.9% 73.5 57.85 23.5% 24.1% 26.0% 570 901 101
43 23.5% 28.9% 35.7% 76.2 59.45 20.2% 21.8% 23.6% 570 1201 101
44 23.1% 28.3% 35.1% 76.4 60.16 20.1% 22.0% 23.7% 570 1201 101
45 31.1% 34.1% 40.0% 97.1 64.20 14.8% 21.3% 22.6% 570 1201 101
46 25.5% 33.5% 39.4% 98.9 64.26 23.7% 21.9% 23.3% 570 1201 101
47 25.9% 33.5% 39.7% 98.7 64.53 23.1% 21.8% 23.3% 570 1201 101
48 23.5% 23.8% 31.9% 52.2 50.93 18.5% 21.2% 23.6% 570 1201 101
49 21.7% 23.8% 31.7% 53.2 53.17 15.4% 21.3% 23.7% 570 1201 101
50 20.4% 23.7% 30.7% 54.0 53.00 17.4% 21.7% 23.8% 570 1201 101
51 20.2% 23.7% 30.4% 54.1 53.36 17.5% 21.8% 23.9% 570 1201 101
52 35.6% 37.9% 48.3% 46.1 54.39 24.2% 26.0% 29.0% 615 1201 101
53 37.1% 43.6% 52.1% 92.4 59.23 28.3% 26.3% 28.5% 615 1201 101
54 37.2% 43.7% 50.9% 92.4 59.10 28.0% 26.6% 28.5% 615 1201 101
55 26.3% 31.3% 40.3% 50.8 49.47 20.8% 26.4% 29.4% 615 1201 101
56 27.1% 31.3% 38.9% 50.3 48.94 21.3% 26.9% 29.4% 615 1201 101
57 37.7% 43.6% 52.0% 92.0 59.82 27.1% 26.3% 28.5% 615 1201 101
58 37.5% 43.7% 52.0% 92.2 59.79 27.0% 26.3% 28.5% 615 1201 101
59 32.1% 48.4% 54.6% 95.5 61.01 25.6% 29.1% 30.8% 615 901 101
60 31.7% 48.4% 55.0% 95.7 61.26 25.3% 28.9% 30.8% 615 901 101
61 32.9% 48.3% 56.9% 95.0 62.22 24.1% 28.6% 30.9% 615 901 101
62 33.5% 48.3% 54.9% 94.6 61.63 25.1% 29.0% 30.9% 615 901 101
63 24.9% 32.0% 42.6% 50.2 59.80 23.7% 23.6% 26.4% 568 861 101
64 28.3% 32.4% 44.5% 49.0 57.87 26.1% 23.4% 26.6% 570 861 101
65 29.8% 32.1% 45.2% 48.4 56.88 27.4% 23.0% 26.5% 570 881 101
66 32.4% 31.9% 44.4% 47.4 56.81 26.7% 23.1% 26.3% 569 881 101
67 32.7% 32.4% 44.8% 47.2 56.77 26.7% 23.4% 26.6% 572 891 101
68 24.4% 29.7% 39.2% 50.4 60.62 21.5% 22.2% 24.6% 568 1061 101
6 24.3% 29.7% 39.7% 50.5 60.19 22.2% 22.0% 24.6% 568 1061 101
7C 28.6% 29.1% 40.3% 48.8 58.51 24.0% 21.4% 24.2% 565 1061 101
71 23.6% 35.4% 47.4% 66.7 65.11 24.7% 21.9% 24.6% 572 1062 101
72 23.5% 35.2% 47.7% 66.7 64.74 25.3% 21.7% 24.6% 571 1056 101
73 25.1% 34.6% 45.8% 66.1 65.54 23.4% 21.6% 24.2% 570 1091 101
74 17.3% 25.3% 34.0% 37.1 53.70 20.9% 23.0% 25.7% 573 1041 101
7 17.3% 25.1% 33.2% 37.2 54.39 19.8% 23.1% 25.6% 575 1093 101
7 21.3% 26.2% 34.6% 35.6 52.78 20.8% 23.7% 26.4% 580 1068 101
7" 20.2% 25.8% 33.2% 36.0 54.02 18.9% 23.7% 26.0% 577 1062 101
256
Table A4.6.4: Summary of Selected I CF B MR Pilot Tests (Sheet 3)
# H2 partial P (kPa) 100%H2 (lux
measured
SLM
H2:C
recovery
ratio
Area
from GC
Membrane area
deduced from flux
Predicted
flux(SLM)
Actual / predicted flux
Reactor
avg, model
Permeate
(expfl)
100%H2 (lux
measured
SLM
H2:C
recovery
ratio
Area
from GC
Membrane area
deduced from flux
Predicted
flux(SLM)
Actual / predicted flux
Reactor
avg, model
Permeate
(expfl)
100%H2 (lux
measured
SLM
H2:C
recovery
ratio (m2) no sweep sweep A=0.06 m2 no sweep sweep
1 137 33 6.2 0.15 0.039 0.047 8.02 77%
2 129 33 6.5 0.15 0.041 0.054 7.41 88%
3 167 23 6.4 0.18 0.034 0.036 10.70 60%
4 177 23 6.4 0.15 0.030 0.035 11.19 57%
5 153 30 7.7 0.18 0.041 0.050 9.47 82%
6 150 30 7.7 0.18 0.042 0.051 9.25 84%
7 211 30 9.1 0.21 0.043 0.043 12.74 71%
8 212 30 9.1 0.21 0.049 0.043 12.83 71%
9 233 34 10.5 0.25 0.047 0.048 13.56 78%
10 145 26 7.1 0.17 0.057 0.045 9.74 73%
11 157 26 7.3 0.17 0.051 0.043 10.41 70%
12 203 30 10.3 0.24 0.068 0.051 12.34 84%
13 200 30 10.4 0.25 0.071 0.052 12.17 85%
14 230 30 9.8 0.23 0.059 0.044 13.65 72%
15 233 30 9.8 0.23 0.058 0.044 13.84 71%
16 197 55 12.1 0.81 0.056 0.083 9.61 126%
17 227 55 12.7 0.84 0.052 0.072 11.47 111%
18 290 55 14.6 0.97 0.048 0.064 14.86 98%
19 285 61 17.0 1.13 0.058 0.081 13.94 122%
20 283 56 17.6 1.17 0.059 0.082 14.33 123%
21 299 101 9.3 0.62 0.038 0.053 11.16 83%
22 262 49 16.7 1.11 0.059 0.077 14.20 118%
23 289 45 13.6 0.90 0.050 0.057 15.42 88%
24 241 42 12.6 0.84 0.056 0.061 13.47 94%
25 258 42 12.6 0.84 0.048 0.056 14.62 87%
26 286 48 14.5 0.96 0.050 0.060 15.53 93%
27 297 101 13.8 0.92 0.064 0.082 11.11 124%
28 278 101 11.4 0.76 0.061 0.072 10.32 111%
29 295 101 11.3 0.75 0.056 0.068 11.07 102%
30 278 101 9.0 0.60 0.046 0.057 10.16 88%
31 252 54 13.2 0.88 0.052 0.067 12.92 102%
32 242 101 9.6 0.48 0.055 0.076 8.20 118%
33 237 48 10.2 0.51 0.042 0.052 12.42 82%
34 238 48 10.4 0.52 0.049 0.053 12.40 84%
35 240 48 9.9 0.49 0.053 0.050 12.54 79%
36 220 48 10.2 0.51 0.063 0.055 11.58 88%
37 226 46 9.3 0.46 0.058 0.048 12.02 77%
38 218 45 10.0 0.50 0.061 0.054 11.68 86%
39 227 45 9.8 0.49 0.063 0.050 12.36 79%
40 227 48 10.0 0.50 0.065 0.052 12.06 83%
41 226 101 9.69 0.32 0.085 0.082 7.43 130%
42 226 57 12.70 0.42 0.073 0.071 11.20 113%
43 272 101 12.26 0.41 0.089 0.080 9.65 127%
44 274 101 11.19 0.37 0.082 0.072 9.73 115%
45 264 51 10.80 0.36 0.070 0.049 13.65 79%
46 271 101 10.69 0.36 0.063 0.070 9.60 111%
47 271 101 11.35 0.38 0.069 0.074 9.57 119%
48 269 40 14.11 0.47 0.066 0.059 15.09 94%
49 270 44 13.95 0.47 0.081 0.060 14.61 96%
50 273 101 12.34 0.41 0.112 0.081 9.68 127%
51 274 101 11.94 0.40 0.108 0.078 9.73 123%
52 330 101 13.32 0.67 0.072 0.066 12.96 103%
53 329 101 16.71 0.56 0.075 0.081 12.93 129%
54 331 101 14.28 0.48 0.065 0.069 12.99 110%
55 335 101 16.82 0.56 0.110 0.081 13.18 128%
56 338 101 14.40 0.48 0.091 0.068 13.31 108%
57 329 55 16.61 0.55 0.059 0.060 17.13 97%
58 329 55 16.42 0.55 0.058 0.060 17.12 96%
59 270 101 12.92 0.43 0.095 0.079 10.19 127%
60 269 101 13.85 0.46 0.103 0.085 10.15 136%
61 268 57 17.15 0.57 0.090 0.076 14.06 122%
62 270 54 13.85 0.46 0.068 0.059 14.47 96%
63 215 55 12.8 0.64 0.075 0.075 10.80 119%
64 215 57 14.7 0.73 0.079 0.089 10.65 138%
65 218 49 15.8 0.79 0.074 0.087 11.61 136%
66 217 52 15.1 0.75 0.074 0.086 11.30 133%
67 223 52 15.1 0.75 0.073 0.083 11.61 130%
68 248 101 11.3 0.57 0.090 0.086 8.50 133%
69 247 101 11.9 0.59 0.090 0.091 8.46 141%
70 242 52 13.2 0.66 0.061 0.068 12.36 106%
71 247 55 14.5 0.73 0.066 0.074 12.44 117%
72 244 56 15.1 0.76 0.068 0.079 12.18 124%
73 250 38 13.5 0.67 0.055 0.059 14.36 94%
74 253 101 10.3 0.52 0.087 0.076 8.81 117%
75 266 101 9.5 0.4a 0.081 0.065 9.41 101%
76 268 38 10.1 0.51 0.046 0.041 15.42 66%
77 264 38 8.9 0.44 0.044 0.037 15.19 59%
Average 0.075 0.059 117%93%
Std. Deviation 0.009 0.015 0.15 0.21
257
Table A4.6.5: Calculation of solids circulation in pilot reactor from helium tracer tests
(Correlations for solids flux for horizontally and vertically panels presented in Figure 3.20)
Units C H 4 H
2
0 N
2
Total
Reactor feed rate (SLM) SLM 42 126 6.6 175
Reactor feed rate (kg/h) kg/h 1.80 6.08 0.50 7.88
Density of feed at 550C,T 100kPa (p
f
) kg/m
3
2.76 Ideal gas
Particle density (p
p
) kg/m
3
2150 NiO catalyst material
Reactor feed gas flow (Q
core
) m
3
/s 8.41E-4 Assume 100%flows to core
Flow area of reactor core (A
core
) m
2
0.0048
Flow area of reactor annulus (A
ann
) m
2
0.0074
Superficial gas velocity in core (U
core
) m/s 0.175 = Qcore 1 Acore, at core entry
Solids voidage at U
m
/(e
m
f) - 0.5 Assumed value
Fraction of measured [He] in core
compared to annulus
- 0.12
Assume that solids entering
core carry gas with [He]
measured at mid-height
annulus
Solids circulation rate (m
pcore
) kg/s 0.22 = 0.12 (Qcore / e
mf
) (p
p
1 s
mf
)
Average downward velocity in annulus m/s 0.027 = 0.12 (Qcore / s
mf
) 1 A
am
Solids fluxup core (G
pcore
) kg/m
2
s 45 Wlpxore / ACOre
Product of (Ucore Pp)
kg/m
2
s 377 Scaling variable
Predicted solids flux from cold model
experimentation (G
pC0
re)
kg/m
2
s
28
Horizontal slotted panels (eq.
5.2)
Predicted solids flux from cold model
experimentation (G
pC0
re)
kg/m
2
s
42
Vertically slotted panels (eq
5.1)
Table A4.6.6: Data from ATR experiments with 0
2
:C molar ratio varied from 0 to 0.6
# Reacto r temperatures (C) Reacto r Heater duty (kW) Feed flo w (SLM)
Co re Splash Freebo ard pressure Preheater Reacto r CH4 H20 N2 Air
average zo ne (kPa)
1 558.50 559 484 1081 1.794 4.2 20.05 60.15 3.2 0.0
2 556.25 560 487 1137 1.872 3.8 20.05 60.15 3.5 11.4
3 556.50 569 492 1186 1.872 2.6 20.05 60.15 5.6 22.9
4 555.50 565 197 1082 1.872 1.8 20.05 60.15 6.7 33.9
5 556.00 575 499 1135 2.34 1.4 20.05 60.15 6.9 45.6
6 553.25 571 498 1110 2.73 1.8 20.05 60.15 7.3 45.6
7 560.75 583 505 1132 2.574 0 20.05 60.15 7.9 58.2
8 561.00 585 507 1133 1.56 0 20.05 60.15 7.6 58.2
# Permeate Reacto r off gas (GC) Steam to 02 to H2 to
Flo w [H2] H2 flow H2 N2 CO CH4 C02 CH4 carbo n carbo n carbo n
(SLM)
[H2]
(SLM) co nv. ratio ratio ratio
1 21.5 47.49 10.19 40.4301 8.1737 0.3483 33.6113 17.4366 34 . 6% 3.0 0.000 0.508
2 21.8 47.86 10.44 32.4328 26.0142 0.3836 25.392 15.774 38. 9% 3.0 0.119 0.521
3 21.0 47.21 9.92 25.376 40.4261 0.2202 19.2968 14.6809 4 3. 6% 3.0 0.240 0.495
4 21.5 47.21 10.16 23.105 48.1202 0.2161 14.5713 13.9874 4 9. 4 % 3.0 0.355 0.507
5 20.2 45.89 9.27 20.7149 54.0275 0.1667 11.4451 13.6458 54 . 7% 3.0 0.478 0.463
6 22.4 44.86 10.04 21.7646 53.4657 0.1599 11.1439 13.4658 55. 0% 3.0 0.478 0.501
7 22.1 44.10 9.75 19.1315 58.932 0.1628 8.3946 13.3791 61. 7% 3.0 0.610 0.486
8 21.1 47.14 9.97 19.4709 58.6093 0.1663 8.4454 13.3081 61. 5% 3.0 0.610 0.497
258
Table A4.6.7: Temperature profile of the reactor core during high temperature ATR tests
(Run #6, NG feed = 20 SLM, S:C = 3.0, note that catalyst activity was low for these tests)
02 : C ratio 0.15 0.3 0.45
Po int Co re 1 Co re 2 Co re 1 Co re 2 Co re 1 Co re 2
D (to p) 64 7. 0 64 6. 5 648. 0 64 8. 0 653. 0 658. 5
C 64 4 . 5 64 8. 5 642. 5 64 7. 0 674 . 0 652. 0
B - 64 6. 0 - 64 1. 0 - 64 4 . 5
A (bo tto m) 635. 5 64 9. 0 646. 0 - 656. 0 -
50%
40%
c
o
E 30%
CD
>
C
o
o
20%
10%
0%
X equilibrium (no membranes)
sweep
no sweep
550 570 590 610 630 650
Temperature (C)
Figure A4.6.1: Measured and predicted methane conversion as a function of reactor temperature
(1,060 kPa, steam-to-carbon = 3.0, run #6, predicted conversion is equilibrium with no H
2
removal, note that catalyst activity is low for these data)
50%
40%
c
o
'jn 30%
>
c
o
o
rf 20%
I
O
10%
0%
no sweep
sweep
X Equilibrium (no membranes)
2.0 2.5 3.5 4.0 3.0
S:C ratio
Figure A4.6.2: Methane conversion as function of steam-to-carbon ratio, reactor temperature and
sweep gas (1,060 kPa, 570C, run #6, catalyst activity is low in these tests)
259
20
^ 15
_J
W
x 10
X
* *
X s
K
- *
R
X
X
X
I
s
X
\ *
X
10 15 20 25 30 35 40 45
Natural gas f eed rate ( SLM)
Figure A4.6.3: Hydrogen flux as a function of natural gas feed rate for all data in Table A4.6.4
260
Appendix 4.7 - Microreactor Data
Table A4. 7. 1: Microreactor catalyst test data
Catalyst: 0.3 g of catalyst mix (50% crushed NiO, 50% alumina)
Conditions: 550C, 201 kPa
Feeds: 30 Nml/min CH4
105 Nml/min H20 (S:C = 3.5)
30 Nml/min H2
Space Vel: 99,400 1/h (based on feed at operating conditions)
Original NiO NiO after 1st run NiO after 3rd run
Time CH4 Time CH4 Time CH4
(hour) conversion (hour) conversion (hour) conversion
0.92 48.6 0.53 44.90 0.48 44.76
1.42 46.7 1.0 46.31 1.03 44.88
1.92 46.3 1.68 45.25 1.72 43.38
5.9 46.1 3.03 45.06 2.48 44.38
6.57 44.7 4.23 44.19 3.47 44.36
19.09 45 20.10 45.15 4.23 43.91
19.59 44.9 23.72 44.71 20.57 39.70
20.22 44 28.40 44.21 22.52 39.70
21.92 44.9 44.43 43.35 24.52 39.35
30.47 44.3 46.85 43.52 26.52 40.56
30.97 44.3 48.55 43.80 28.12 39.88
43.92 43.1 50.57 42.95 44.47 36.19
44.5 42.8 52.38 42.60 46.55 34.77
45 43.8 68.28 43.53 48.52 35.20
48.92 42.8 50.65 34.36
49.45 42.4 52.28 34.00
53.22 41.6 68.30 31.10
53.92 41.6 70.93 30.85
54.65 42.1 72.65 30.65
65.58 40.3 140.32 20.72
66.08 40.6
66.58 38.9
69.83 39.4
70.45 39.3
72.17 39.2
72.67 39.3
261
Table A4. 7. 2: Data from virgin A T R microreactor tests
to
to
Operating
Mode
Date Time Hour
Bed temp fC) GC analysis Exit flow
(s/60ml)
CH4 Conv
(%)
Carbon
Balance
H2:C
Operating
Mode
Date Time Hour
T1 T2 T3 AvgT H2 CO CH4 C02
Exit flow
(s/60ml)
CH4 Conv
(%)
Carbon
Balance
H2:C
ATR
06/13/05 12:10 0.00
ATR
06/13/05 14:02 1.87 511 557 583 550 57.7 1.43 15.45 25.42 13.53 63.48 94.9 1.29
ATR
06/13/05 15:09 2.98 508 565 583 552 57.96 1.41 15.68 24.95 13.57 62.70 93.8 1.29
ATR
06/13/05 16:28 4.30 508 562 584 551 57.85 1.37 16.18 24.6 13.49 61.61 95.0 1.30
ATR
06/14/05 8:12 20.03 502 536 615 551 56.23 1.26 19 23.46 14.13 56.54 90.4 1.16
ATR
06/14/05 11:59 23.82 503 540 617 553 55.83 1.22 19.33 23.63 13.68 56.25 97.1 1.23
ATR
06/14/05 16:20 28.17 503 539 619 554 55.13 1.31 20.05 23.51 13.62 55.32 99.4 1.22
ATR
06/15/05 9:59 45.82 502 540 604 549 55.3 1.24 20.4 23.05 13.73 54.35 97.5 1.21
SMR
06/15/05 11:05 46.92 517 517 517 517 67.39 1.07 23.82 7.72 15.37 26.95 118.4 2.44
SMR
06/15/05 12:13 48.05 550 550 550 550 72.94 2.11 15.09 9.86 14.88 44.24 101.5 2.73
SMR
06/15/05 13:18 49.13 551 551 551 551 72.53 2.10 15.72 9.65 14.86 42.77 103.2 2.71
SMR
06/15/05 14:56 50.77 551 551 551 551 72.39 2.10 15.94 9.57 14.92 42.27 103.3 2.70
SMR
06/15/05 15:50 51.67 551 551 551 551 72.47 2.08 15.83 9.62 14.92 42.50 103.0 2.70
SMR
06/16/05 9:10 69.00 550 550 550 550 72.49 2.17 15.95 9.38 . 14.92 42.00 102.8 2.70
SMR
06/16/05 11:06 70.93 550 541 557 549 72.30 2.16 16.16 9.37 14.77 41.64 104.6 2.72
SMR
06/16/05 13:00 72.83 551 543 558 551 72.41 2.17 16.04 9.38 14.81 41.86 104.0 2.72
SMR
06/16/05 16:30 76.33 550 542 558 550 72.28 2.18 16.19 9.36 14.68 41.62 105.4 2.74
SMR
06/17/05 9:02 92.87 550 544 560 551 72.13 2.23 16.50 9.14 14.99 40.80 103.7 2.68
SMR
without H2
06/17/05 10:13 94.05 547 537 560 548 67.62 3.03 14.97 14.37 17.58 53.75 102.7 2.14
SMR
without H2
06/17/05 11:07 94.95 548 538 560 549 67.70 3.07 14.85 14.38 17.76 54.02 101.5 2.12
SMR
without H2
06/17/05 12:01 95.85 548 538 560 549 67.71 3.07 14.86 14.36 17.66 53.98 102.0 2.13
SMR
without H2
06/17/05 12:36 96.433 548 538 560 549 67.66 3.07 14.90 14.37 17.67 53.93 102.1 2.13
SMR
without H2
06/17/05 14:10 98 549 538 561 549 67.72 3.05 14.89 14.34 17.62 53.87 102.2 2.13
02 cycling
every one
mintue
06/17/05 14:40 98.5 0 51.85 1.54 29.14 17.47 39.48
02 cycling
every one
mintue
06/17/05 14:55 98.75 0 52.32 1.55 28.99 17.14 39.20
02 cycling
every one
mintue
06/17/05 15:10 99 0 53.28 1.46 28.27 17.00 39.50
02 cycling
every one
mintue
06/17/05 15:25 99.25 0 52.97 1.56 27.80 17.66 40.88
ATR
06/17/05 16:00 99.833 501 546 608 552 50.42 1.49 25.31 22.79 14.33 48.96 99.80 1.95
ATR 06/17/05 16:41 100.52 502 541 605 549 50.02 1.48 25.69 22.81 14.62 48.60 96.72 1.90
ATR
06/17/05 17:28 101.3 501 541 609 550 49.81 1.5 25.91 22.79 14.49 48.39 98.86 1.91
Appendix 4.8 - TGA Analysis of SMR Catalyst
Thermo-grayimetric analysis (TGA) was performed on three S MR catalyst samples (NiO, Siid-
Chemie G-91 5/8" x 1/4" EW, see Table A5.3.1). This work was carried out in a Shimadzu TGA50H.
A sample of crushed catalyst (~18 mg) was heated in a 50 ml/min gas flow of mixed air / nitrogen
from ambient temperature to 800C at a rate of 10C/min (see Figure A5.3.1 for temperature profile).
The normalized weight loss / gain profile of the three samples are presented in Figure A5.3.2
Table A4. 8. 1: T G A S MR catalyst samples
# Description
Alumina
dilution
Sample
weight (mg)
Comments
1 Fresh catalyst None 16.88 Crushed from spoked pellets
2
I CF B MR catalyst after Apri l
20 2004 run
50% 17.72
Grey-black powder. Activity
shown to O Kin microreactor
I CF B MR catalyst after Apri l
20 2004 run
tests
3
I CF B MR catalyst after last
Ni O run
50% 18.75
Grey-black powder. Activity
known to be low
1000
O 800
0)
^ 600
ns
E
* 200 -
0 ^ : , , , , , ,
0 20 4 0 60 80 100 120 140 160
Time (min)
Figure 4.8.1: Temperature profile of T G A tests
The fresh Ni O catalyst showed a steady weight loss over most of the temperature range. The T GA
weight profiles for the two used catalysts were almost identical and showed a slight weight increase,
perhaps due to oxidation of nickel. The time derivative of the weights for sample #1 (fresh catalyst)
and sample #3 (used catalyst) are presented in Figures A4.8.3 and A4.8.4 respectively. The profile for
the other used S MR catalyst sample (#2) is very similar. As can be seen, the fresh sample lost weight
at a fairly consistent weight, where the derivative profile for the used catalyst peaked around 400C.
263
1.02
| 0.96
o
z
0.94
3. After 3rd run
2. After 1st run
1. Fresh NiO
200 300 400 500 600 700 800
Temperature (C)
0 100
Figure A4.8.2: TGA weight profiles of NiO samples, normalized to initial sample weight
0.0010
8ffl0
-0.0010
Temperature (C)
Figure A4.8.3: TGA differential weight profiles of sample #1 (fresh NiO catalyst)
0.0010
8<D0
-0.0010
Temperature (C)
Figure A4.8.4: TGA differential weight profiles of sample #3 (after final ICFBMR run)
264
Appendix 4.9 - XRD Analysis of SMR Catalyst
X-ray diffraction analysis (XRD) was performed on SMR catalyst samples to identify the form of
nickel in the new and spent reforming catalyst in order to better understand the mode of catalyst
deactivation. XRD is a crystallography technique in which the pattern of diffracted x-rays from a
powdered sample are analysed to identify the nature of the crystal lattices. The analyses were carried
out in Siemens Diffraktomer D5000 with a cobalt detector operating at 40 mA / 35 kV. Samples were
ground to a fine slurry in acetone and then deposited as a thin film on a glass slide. After drying, the
slides were placed in the XRD machine and subjected to the x-ray source over an angle of 8 to 80.
The spectrum was analysed using a commercial software package (XRD Commander) and matched
to a spectra database (EVA). The same three samples analysed in the TGA apparatus where analysed
in the XRD machine (samples 1 - 3 in Table A4.9.1).
# Description Alumina dilution Comments
1 Fresh SMR catalyst None Crushed from spoked pellets
2
ICFBMR catalyst after April 20 2004
run
50%
Activity shown to OK in microreactor
tests
3 ICFBMR catalyst after last NiO run 50% Activity known to be low
o
O
l< I
I M l ! I h i t ,
i nAI'MII$fy