(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization I
International Bureau
(10) International Publication Number
(43) International Publication Date
WO 2014/013061 Al
2 3 January 2014 (23.01.2014) P O P CT

(51) International Patent Classification: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
H01M 8/06 (2006.01) H01M 8/04 (2006.01) DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
C01B 3/00 (2006.01) H01M 8/12 (2006.01) HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KN, KP, KR,
KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
(21) International Application Number: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
PCT/EP2013/065321 OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC,
(22) International Filing Date: SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
19 July 2013 (19.07.2013) TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(25) Filing Language: (84) Designated States (unless otherwise indicated, for every
English
kind of regional protection available): ARIPO (BW, GH,
(26) Publication Language: English GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
(30) Priority Data: UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
PA 2012 70450 20 July 2012 (20.07.2012) DK TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, FT, LT, LU, LV,
(71) Applicant: TOPS0E FUEL CELL A/S [DK/DK]; MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
Nyni0llevej 66, DK-2800 Kgs. Lyngby (DK). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).
(72) Inventor: ROSTRUP-NIELSEN, Thomas; Geelsvej 37,
DK-2840 Holte (DK). Published:
(81) Designated States (unless otherwise indicated, for every — with international search report (Art. 21(3))
kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,

(54) Title: METHOD AND EASY MAINTENANCE REACTOR ASSEMBLY FOR THE PROCESSING OF HYDROCARBON
FUELS

o
©
(57) Abstract: Method and reactor assembly for the processing of hydrocarbon fuels by pre-reforming to produce an anode feed gas
o for use in connection with a fuel cell system, said method comprising the steps of a) treating the hydrocarbon fuel with steam, with
steam and hydrogen or with syngas, or with any combination thereof, in a pre-reformer system in order to convert the fuel to syngas
o and to remove at least part of the sulfur species from the fuel, and b) feeding the syngas obtained in step (a) to the anode inlet of a
fuel cell system, wherein the pre-reformer system comprises two or more interconnected treatment zones, each of said zones being
individually replaceable.
Method and easy maintenance reactor assembly for the pro
cessing of hydrocarbon fuels

The present invention relates to a method and reactor as-

sembly for the processing of hydrocarbon fuels including
pre-ref orming to produce an anode feed gas for use in con
nection with a fuel cell system. Furthermore, the invention
relates to an apparatus suitable for carrying out said
method, and it also relates to an internal reforming fuel
cell system comprising a reactor assembly with intercon
nected treatment or reaction zones.

WO 03/065488 A l describes a fuel cell system comprising a

reformer which contains one zone or i s divided into two
zones with a subsequent desulfurizer placed before the fuel
cell anode. The purpose of the reformer i s to act a s a
means of exercising thermal management of the fuel cell b y
being able to obtain different levels of methane in the e f
fluent. The fuel cell can internally reform e.g. methane by
an exothermal reaction, and thus the methane content of the
reformer effluent will affect the level of cooling b y in
ternal reforming. The reformer i s an autothermal reformer
(ATR) combining catalytic partial oxidation and steam re
forming reactions. Said ATR i s fed with fuel, oxidant (i.e.

air) and steam (anode recycle) . This W O document teaches

that, depending of the sulphur content of the fuel, it may
b e desirable to include a desulfurizer unit to remove sul
fur compounds from the ATR effluent, because sulfur com
pounds may poison the catalyst used for internal reforming
in the fuel cell. Such a desulfurizer includes a hydrogena-
tion catalyst to generate ¾ S and an ¾ S adsorbent bed. A
conventional desulfurizer unit, which consists of a hydro-
genation catalyst converting sulfur compounds into ¾ S and
a subsequent sulfur adsorbent to remove the ¾S, may b e em
ployed. The hydrogenation step requires hydrogen to b e sup
plied together with the fuel. It i s desirable to desulfu-
rize to a level below 1 ppm (wt) and preferably below 0.2
ppm (wt) .

The solid oxide fuel cell (SOFC) system according to the

invention has a reformer divided into two or more zones for
reasons which are completely different from those of the
above W O document. That document seeks to deal with sulfur
b y conventional hydrodesulf urization (HDS) a s practised in
large industrial plants where hydrogen i s needed (which i s
complicated in smaller scale plants) b y removing most of it
through a pre-treatment b y HDS prior to the fuel cell sys
tem and removing the rest downstream from the ATR b y yet
another HDS step. According to the present invention, the
use of HDS i s avoided b y using a suitable reforming cata
lyst a s both a reforming catalyst and a sulfur removal
means. In the W O document the reformer i s divided into two
zones to separate a catalytic partial oxidation (CPO) cata
lyst from a reforming catalyst. According to the present
invention, the reforming reactor i s divided into zones to
obtain a means of replacing parts of the catalyst a s it
gets poisoned b y sulfur. Also, the W O document describes a
type of autothermal reforming which i s different from the
type used in the present invention. B y practising au tother
mal reforming according to the W O document, a loss in elec
trical efficiency i s introduced, because oxygen entering
the ATR will consume part of the fuel, which will then b e
unavailable for power production, whereas the reforming
method of the present invention only changes the chemical
composition of the fuel, whereby the full power producing
potential i s preserved. In the W O document, the various
components of the fuel cell system are combined with con
ventional gas supply conduits, while according to the pre-
sent invention the reformer zones are connected using spe
cial attachments, such a s isolation valves and quick con
nects, designed for easy replacement.

WO 00/78443 A l describes a system comprising several re-

formers for providing a pure hydrogen stream to b e used
with fuel cells. Hydrocarbon feeds generally contain impu
rities, such a s sulfur, which must b e removed prior to in
troducing the feedstock to the steam reforming zone. The
necessary pre-processing module depends on the composition
of the feedstock. ¾ S in natural gas can b e removed by
chemisorption, using e.g. zinc oxide. Liquefied petroleum
gas (LPG) contains very little sulfur and can thus b e used
directly, although a guard bed with an adsorbent may b e in
cluded. Naphtha requires a multi-stage treatment which re-
quires HDS with hydrogen forming ¾ S from the sulfur impu
rities and subsequently a stage to remove ¾S. Preferably
the sulfur concentration in the desulfurized feedstock will
b e less than about 1 0 ppm (wt) , more preferably less than
about 1 ppm (wt) . The above W O document describes a system
in which a pre-processed fuel i s mixed with steam before
entering a pre-ref orming zone in intimate thermal contact
with a first heat exchange zone, which transfers heat to
the pre-ref orming zone. Subsequently the resulting stream
i s led to a partial oxidation zone together with an oxygen-
containing stream (e.g. air), and b y passage over a partial
oxidation catalyst a partial oxidation product i s formed.
The partial oxidation zone i s followed b y a steam reforming
zone and finally b y a CO conversion reactor, generating a
hydrogen-rich stream. The system of the above WO document
has several reforming-type zones, each serving a different
purpose. None of these zones can be taken out of operation
without stopping the system, i.e. they all have to be pre
sent for the system to operate. The reactor assembly of the
present invention comprises several reforming zones carry
ing out the same reaction, and thus the system can be oper
ated in the absence of any of these zones.

In US 2009/0169931 A l a method for increasing the fuel uti

lization in a fuel cell system i s described, whereby the
challenge of limitation of cell voltage and uniform fuel
distribution i s met. The method involves having a C O 2 re-
moval unit in the anode recycle, which may also remove part
of water and a portion of sulfur compounds from the fuel
gas. The method may include a pre-reformer and/or a reform
er in front of the fuel cell. The purpose of the reformer
and the pre-reformer i s to convert hydrocarbon fuels into a
hydrogen gas to be fed to the fuel cell. According to this
U S application, a pre-reformer will remove higher hydrocar
bons and thus prevent carbon formation in a downstream re
former or fuel cell. The focus of the U S application is

however completely different from that of the present in-

vention. Furthermore, the purpose served b y the reforming
steps i s similar in effect to the conversion of hydrocar
bons, but the handling of sulfur i s completely different.
According to the present invention, sulfur i s removed b y
means of the pre-ref orming system, which i s designed to
handle the sulfur load, while in the U S application it i s
attempted to remove sulfur from the system b y means of the
C O 2 removal unit, and the impact of sulfur on the reforming
step i s not addressed.

Finally, EP 1 245 532 A 2 describes a method for generating

a reformed gas with hydrogen to be used e.g. in a fuel cell
b y feeding a fuel, steam and air to a reforming system com
prising two or more reforming departments, each with two
reaction zones, i.e. a partial oxidation zone and a reform
ing zone. Each of the reforming departments can be re-
placed. They are shaped a s tubes and external heating is
supplied b y a hot gas, e.g. from a combustor passing be
tween the tubes and the reformer housing. The object i s to
obtain a system which can start-up fast b y increasing the
temperature rapidly. Moreover, like the system according to
the present invention it should be compact and easy to
maintain. However, the system according to the invention
differs from the system of the above E P application in a
number of respects. First of all, the system of the E P ap
plication uses air a s part of the feed to any reforming
section, which the system of the invention does not. Using
air lowers the yield of hydrogen, because part of the fuel
i s combusted, and therefore the possible electrical effi
ciency i s lowered. Secondly, the system of the E P applica
tion has two different types of reforming reaction in each
reforming tube, i.e. partial oxidation and reforming, while
the system of the present invention has reforming a s the
only reaction type. Thirdly, the system according to the
invention acts a s both a reformer and a sulfur removal
unit, whereas the E P application does not address sulfur,
and finally the E P application deals with externally heated
reforming zones, while the system of the invention can be
adiabatic .
The present invention differs from the prior art in that
the pre-ref orming system i s used deliberately a s a sulfur
removal step in addition to carrying out the reforming re
action, and the present invention presents means of design
ing the pre-ref orming system to function a s such.

More specifically, the present invention concerns a method

for the processing of hydrocarbon fuels including a pre-
reforming step to produce an anode feed gas for use in con
nection with a fuel cell system, said method comprising the
steps of

(a) treating the hydrocarbon fuel with steam, with

steam and hydrogen or with syngas, or with any com
bination thereof, in a pre-reformer system in order
to convert the fuel to syngas and to remove at
least part of the sulfur species from the fuel, and

(b) feeding the syngas obtained in step (a) to the an

ode inlet of a fuel cell system,

wherein the pre-reformer system comprises two or more in

terconnected treatment zones, each of said zones being in
dividually replaceable.

Further, the invention relates to an apparatus suitable for

carrying out the above method, said reactor assembly com
prising a reactor assembly, wherein the hydrocarbon fuel i s
treated with steam, with steam and hydrogen or with syngas,
or with any combination thereof to remove at least part of
the sulphur species from the fuel while also converting the
reactor feed to a suitable syngas for an internal reforming
fuel cell system.

Additionally, the invention relates to an internal reform-

ing fuel cell system comprising a reactor assembly with in
terconnected treatment or reaction zones.

According to the invention, the reactor assembly comprises

a pre-reformer assembly that i s characterised in that it
consists of a number of interconnected treatment zones,
each of said zones being individually replaceable or re
placeable in groups or replaceable a s one unit when cata
lyst poisoning makes a replacement necessary.

The hydrocarbon fuel to be used a s feed stream typically

contains sulfur. If the sulfur content i s high, the fuel
may be desulfurized before entering the reactor assembly,
but in case of moderate sulfur levels the fuel may be fed
to the reactor assembly without prior desulf urization .
Irrespective of the actual sulfur content of the fuel, a
first treatment zone will always receive the heaviest load
of sulfur, and therefore the first zone will need to be re
placed more often than subsequent zones due to catalyst
poisoning. Thus, the first zone may have a rather limited
life time, whereas the subsequent zone(s) will be poisoned
to a more limited extent, and therefore the life time will
be longer.

A final zone must be sufficiently large, i.e. have a suffi-

cient capacity to convert the fuel to syngas to such an ex
tent that downstream carbon formation, e.g. in a solid ox
ide fuel cell (SOFC) , can be avoided. In designing the size
of this final zone any pre-conversion obtained in the up
stream zones may be taken into account, such that the final
zone in itself must not necessarily be large enough to ob
tain the desired conversion alone.

The reactor assembly may be equipped with a zone by-pass

system. This system will allow by-pass of the individual
reactor zones. In this way it i s possible to replace indi
vidual reactor zones or groups of reactor zones during op-
eration of the system. The replaced zones can subsequently
be brought back into operation. Before being brought back
into operation, the zones may have been heated to a suita
ble temperature, e.g. b y electrical heating, gas convective
heating, heating from surroundings (e.g. b y convection

and/or b y radiation), or b y passing a suitable heating gas

through the reactor zones.

The individual zones may be designed for various intended

life times, e.g. from 100 hours to five years or 1-75 % of
the product life time. The final zone(s) may be designed to
last for the full product life time, and only the upstream
zones are designed for a shorter life time, and thus will
need replacement.

The zones may be housed in separate containers or in the

same container, and the containers are preferably mounted
outside the main box housing the reactor assembly. Zones
not needing replacement could be placed inside the main box
housing of the reactor assembly. In order to facilitate
zone replacement the replaceable zones can be mounted on
the system with quick connects or similar easy-to-connect
and disconnect features that make cutting welds or similar
unnecessary. Thereby, maintenance of the zones, especially
replacement of the zone materials (catalyst, or reactor,
reactor sections, or cartridges etc.), becomes much easier
compared to prior art process designs. Because of the easy
access to the zones, the service costs become significantly
lower than hitherto possible.

When in operation, pre-ref orming catalysts contained in the

reactor assembly will inevitably deactivate over time due
to ageing and a slow poisoning of the catalyst, e.g. from
sulfur. Therefore, to operate the reactor assembly accord
ing to the invention in an optimal way, it i s important to
be able to monitor the individual parts thereof. The moni
toring can thus guide the operation e.g. with respect to
activation of zone by-pass, zone or zone group replacements
etc .

This can for instance be done using the so-called Zg deac

tivation plot to evaluate the deactivation rate. Based on
the measured temperature profile for the pre-reformer bed
reported over a period of time, the Zg deactivation points
can be calculated and depicted in a o deactivation plot
for evaluation of the pre-reformer performance.

A s an example, further monitoring methods could be:

1. Monitoring of temperature differences along the zones,

a s these would give information about catalyst activi
ty.

2. Operating hours. Zone replacement could be scheduled

to be performed after a certain time on stream.
 3. Fuel flow rate. Zone replacement could be scheduled to
be performed after a certain amount of processed fuel.

. Zone replacement could be scheduled to be after a cer-

tain amount of system age and possibly coincide with
other system maintenance.

5. Monitoring Zone pressure drop. An increase could indi

cate that by-pass and/or replacement will be advanta-
geous .

Another problem, which i s often encountered, i s the problem

with increased pressure drop in the reactor assembly. The

increased pressure drop can stem from gum formation, which
i s a build-up of material originating from the fuel on the
catalyst .

Gum typically forms when the temperature in the reaction

zone falls below a certain limit. Typically, when subject-
ing hydrocarbons steam reforming reactions over a pre-
reforming catalyst, the temperature initially drops due to
the endothermic reaction. One way of avoiding or limiting
the temperature drop, i s to have the hydrocarbon fuel mixed
with anode recycle from the fuel cell, which contains sig-
nificant amounts of CO. This will result in the exothermic
methanation reaction taking place, which provides heat to
balance the endothermic steam reforming of the hydrocar
bons .

The pressure drop, ∆Ρ , from zone to zone can be monitored

to detect the presence of gum formation or other phenomena
resulting in pressure drop build up (e.g. particulate mat-
ter) . When the pressure drop increases in a given zone,
this zone can b e bypassed while it i s replaced. This way an
effective use of the pre-reformer assembly i s obtained.

The individual zones or beds of the reactor assembly do not

necessarily contain the same catalyst. Thus, in a preferred
embodiment of the reactor assembly according to the inven
tion, the reactor assembly (e.g. a pre-reformer) comprises
one or more beds containing mixed catalysts. It i s also
possible to have two or more bed types, each containing a
different catalyst, e.g. a catalyst (1) primarily for re
forming activity, a catalyst (2) primarily for hydrogena-
tion or hydrocracking and a catalyst (3) for sulfur rem ov
al. Further, an individual bed may b e graduated, such that
e.g. the first part mainly contains a catalyst (2) (e.g. a
Haldor Topsoe A/S TK type catalyst), the middle part mainly
contains a catalyst (3) (e.g. ZnO such a s a Haldor Topsoe
A/S HTZ type catalyst) and the last part mainly contains a
reforming catalyst (e.g. a Haldor Topsoe A/S pre-reformer
type catalyst such a s AR-401) .

In a preferred embodiment of the reactor assembly according

to the invention the pre-ref orming bed system i s provided

with integrated means for hydrodesulf urization (HDS) , ena-

bling the fuel to b e converted to a more suitable feed for

an internal reforming fuel cell system.

In another embodiment of the reactor assembly according to

the invention, the pre-ref orming bed system i s provided

with replacement or bypass options based on a monitoring

equipment to give guidance regarding when to effect re
placement of individual beds in the system. The monitoring
i s intelligent in the sense that it uses various inputs.
That could be (but i s not limited to) measurements of:

Pressures

Pressure differences

Temperatures

Temperature differences

Fuel flow

Operating time

By-passes engaged

Cumulative operating time of an individual reactor

zone

Fuel cell stack performance parameters (e.g. voltage,

pressure drop, current, temperatures etc.)

System recycle flow rates and recycle locations

Fuel properties

to compute the right recommendation for the operator of the

reactor assembly.

In another embodiment of the reactor assembly according to

the invention, the reactor assembly i s provided with means
for controlling the reactor assembly temperature. Depending
on the hydrocarbon fuel, recycle gas and other parameters
it can be advantageous to operate a pre-ref orming bed sys
tem in either or a combination of modes:

• Cooled

• Adiabatic

• Heated
For instance it can be advantageous to operate the first
part of the reactor assembly slightly heated in order to
avoid gum formation. Subsequently the following zones can
be operated adiabatically in order to provide a fuel stream
for the fuel cell with a relatively high content of me
thane, or heated to obtain an equilibrated gas at a higher
temperature with a lower content of methane. The amount of
heating could be an integral part of the operating strategy
of the entire system, a s the content of methane in the fuel
influences the fuel cell stack cooling. A fuel cell stack
will need an increased amount of cooling a s the stack ages
and the internal resistance increases. This additional
cooling could come from increased air flow on the cathode
side, or it could to some extend be provided b y increasing
the methane content of the fuel cell fuel, which can be ob
tained b y lowering the final temperature from the reactor
assembly. The methane content i s basically determined by
the chemical equilibrium for the steam reforming reaction
and the water gas shift reaction.

In the following examples, the invention will be described

in more detail with reference to the accompanying drawings.
In the drawings, the following symbols and abbreviations
are used:

The feed lines 1 and 2 are used to supply a hydrocarbon

feed (line 1) and optionally a supplementary gas in the
form of steam, steam + hydrogen or syngas (line 2 ) .

A i s the anode of a fuel cell system, and R i s a reactor

assembly. Furthermore, M.S. in Fig. 1 0 and Fig. 11 is a

monitoring system, and M in Fig. 7, Fig. 8 and Fig. 9 is a

main box housing. The abbreviation H at the arrows in Fig.
1 1 means "heat".

Example 1

Fig. 1 i s a general view of a reactor assembly R suitable

for treatment of hydrocarbon fuel b y pre-ref orming in said
reactor assembly according to the invention for use in a
fuel cell system.

Example 2

Fig. 2 illustrates a reactor assembly in form of a pre-

reformer divided into two zones (zone 1 and zone 2 ) that
are sized according to different objectives. Thus, zone 1
may be sized to 1-75 % of the product lifetime or to be
tween 100 hours and 5 years due to sulfur poisoning, and
zone 2 i s sized for suitable conversion of the hydrocarbon
feed to syngas. The beds in the zones are each individually
replaceable or replaceable a s a unit.

Example 3

Fig. 3 illustrates an embodiment of the pre-ref orming part

of the reactor assembly divided into several zones (1 to 3)

that are sized according to different objectives. More spe

cifically, zone 1 and zone 2 are each sized to 1-75 % of
the product lifetime or to between 100 hours and 5 years
due to sulfur poisoning, whereas zone 3 i s sized for suita-
ble conversion of the hydrocarbon feed to syngas. The beds
are replaceable individually or a s a unit. The zones can be
by-passed such that a poisoned zone can be taken off line
and be replaced during operation of the pre-ref ormer .

Example 4

In Fig. 4, another embodiment of the reactor assembly ac

cording to the invention i s illustrated, where a hydrocar
bon feed i s mixed with recycled syngas obtained from the
anode exit. Like in Example 3, zone 1 and zone 2 are each
sized to 1-75 % of the product lifetime or to between 100
hours and 5 years due to sulfur poisoning, whereas zone 3
i s sized for suitable conversion of the hydrocarbon feed to
syngas. The recycle can be added to optimally match the
zones in operation and their state. Due to the pressure
drop in the system a means of recycling the syngas must be
applied .

This may require partial cooling before a blower can effec

tively operate.

Example 5

In Fig. 5, still another embodiment of the reactor assembly

according to the invention i s illustrated, where the hydro-
carbon feed i s mixed with syngas obtained from the reactor
assembly (pre-ref ormer ) exit. A s in the previous examples 3
and 4, zone 1 and zone 2 are each sized to 1-75 % of the
product lifetime or to between 100 hours and 5 years due to
sulfur poisoning, whereas zone 3 i s sized for suitable con-
version of the hydrocarbon feed to syngas. The recycle can
be added to optimally match the zones in operation and
their state. Due to the pressure drop in the system a
means of recycling the syngas must be applied. This may re
quire partial cooling before a blower can effectively oper
ate and be made from inexpensive materials.

Example 6

Fig. 6 illustrates a further embodiment of the reactor as

sembly according to the invention, where the hydrocarbon
feed i s mixed with syngas obtained from a combination of
the reactor assembly (pre-ref ormer ) exit and the anode ex
it. Again, zone 1 and zone 2 are each sized to 1-75 % of
the product lifetime or to between 100 hours and 5 years
due to sulfur poisoning, whereas zone 3 i s sized for suita
ble conversion of the hydrocarbon feed to syngas. Here it
i s shown that the two recycle streams use the same piping
system, however, they could also use separate piping allow
ing individual recycle points. The recycle can be added to
optimally match the zones in operation and their state. Due
to the pressure drop in the system, a means of recycling
the syngas must be applied. This may require partial cool
ing before a blower can effectively operate and be made
from inexpensive materials.

Example 7

Fig. 7 illustrates a still further embodiment of the reac

tor assembly according to the invention, where the reactor
assembly i s situated outside the main box housing M (the

box in broken lines) for the fuel cell system to facilitate

easy replacement of zones. Replacement zones are located
conveniently, and in these zones an easy-to-replace mount
ing, such a s quick connects, can be used.
Example 8

Fig. 8 illustrates another embodiment of the reactor assem

bly shown in Fig. 7, where the reactor assembly i s situated
partially inside and partially outside the main box housing
M (the box in broken lines) for the fuel cell system. Zones
needing easy access are located outside the main box hous
ing to facilitate easy replacement of zones, while zones
not intended to be replaced are located inside the main box
housing. Replacement zones are located conveniently, and in
these zones an easy-to-replace mounting, such a s quick con
nects, can be used.

Example 9

In Fig. 9, another embodiment of the reactor assembly ac

cording to the invention i s illustrated, in which the reac
tor assembly i s situated inside the main box housing M (the
box in broken lines) for the fuel cell system, which i s de-
signed such that it i s easy to open and such that the zones
needing replacement are located conveniently, and for quick
and easy replacement easy-to-replace mounting, such a s
quick connects, can be used. In this embodiment, any hot
parts surrounding the fuel cell system are located in a
special well-isolated part of the main box housing (the box
in dotted lines) .

Example 10

Fig. 1 0 illustrates still another embodiment of the reactor

assembly according to the invention, where the system i s
combined with a monitoring system M.S. which guides zone
by-pass, recycle and replacement.

Example 11

Another embodiment of the reactor assembly shown in Fig. 1 0

i s illustrated in Fig. 11, where the system i s again com
bined with a monitoring system which guides zone by-pass b y
monitoring zone pressure drop build-up. The recycle flow
can be matched to avoid temperature drop due to the hydro
carbon steam reforming reaction (endothermic) , because the
recycle gas i s rich in CO which will result in the methana-
tion reaction taking place (exothermic) . If the temperature
drops too much and this i s not compensated for, then there
i s a risk of gum formation. Another means of avoiding the
temperature drop i s b y applying heat (H) from any number of
sources (e.g. electrical), shown a s broken line arrows in
Fig. 11.

Example 12

Fig. 12 illustrates a still further embodiment of the reac

tor assembly according to the invention, where the reactor
assembly i s a pre-reformer divided into several zones
(three zones in the figure) . Each of these zones may con
tain mixed catalysts. The mixture in each zone can be uni
form or graduated. Also the zones may contain different
mixtures of catalysts or only one kind of catalyst. This
can be realised with any number of zones.
Example 13

Fig. 13 illustrates an embodiment of the reactor assembly

according to the invention, where the zones are individual-
ly cooled, adiabatic or heated. The control of the temper
ature can suit many different purposes, such a s the follow
ing :

- Gum formation can be avoided b y keeping the minimum tem-

perature above a certain critical limit.

- The methane content in the final syngas from zone 3 going

to the fuel cell system can be controlled, thereby adjust
ing the amount of cooling obtained b y internal reforming in
the fuel cell system. The more methane present, the more
cooling i s necessary. This can be used instead of or in
combination with an increased cathode cooling air flow rate
and temperature, to keep the desired stack temperature. As
the stack ages or degrades, the cooling requirement in-
creases.

- Graduated catalyst zones (types of catalysts) may operate

best at different temperatures.

Each of the zones in this embodiment can individually be

adiabatic, or they can be cooled or heated, independent of
one another. Therefore, each zone may be provided with
means to change mode during operation of the system.

The exit temperature from zone 3 will determine the gas

composition and especially the methane content. The higher
the exit temperature is, the lower the methane content will
be .
Claims :

1. A method for the processing of hydrocarbon fuels in

cluding a pre-ref orming step to produce an anode feed gas
for use in connection with a fuel cell system, said method
comprising the steps of

treating the hydrocarbon fuel with steam, with

steam and hydrogen or with syngas, or with any com
bination thereof, in a pre-reformer system in order
to convert the fuel to syngas and to remove at
least part of the sulphur species from the fuel,
and
feeding the syngas obtained in step (a) to the an
ode inlet of a fuel cell system,

wherein the pre-reformer system comprises two or more in

terconnected treatment zones, each of said zones being in
dividually replaceable.

2. The method according to claim 1, including the step of

(c) recirculating part of the anode off-gas from the fuel
cell system to the pre-reformer system, preferably to the
inlet of the first treatment zone.

3. The method according to claim 1 or 2 , wherein the pre-

reformer system i s designed so that the pre-ref orming cata
lyst (s) in the treatment zones may be easily replaced.

. The method according to any one of the preceding

claims, wherein the fuel cell system i s a medium to high
temperature fuel cell system operating at approximate tem
peratures above 500°C and below 950°C.

5. The method according to any one of the preceding

claims, wherein the fuel cell system i s a solid oxide fuel
cell system comprising a single solid oxide fuel cell or at
least one solid oxide fuel cell stack.

6. The method according to any one of the preceding

claims, wherein the pre-reformer i s an adiabatic pre-
ref ormer .

7. An reactor assembly suitable for carrying out the

method according to any one of the preceding claims, said
reactor assembly comprising a pre-reformer assembly, where
in the hydrocarbon fuel i s treated with steam, with steam
and hydrogen or with syngas, or with any combination there
of to remove at least part of the sulfur species from the
fuel, and an internal reforming fuel cell system,
wherein the pre-reformer assembly consists of a number of
interconnected treatment zones, each of said zones being
individually replaceable.

8. The reactor assembly according to claim 7 , wherein the

individual treatment zones are designed for various intend
ed life times.

9. The reactor assembly according to claim 7 or 8, where

in a second zone in fuel flow direction has a sufficient
capacity to convert the fuel to syngas to such an extent
that downstream carbon formation can be avoided.
10. The reactor assembly according to any one of claims 7 -
9, wherein the treatment zones are housed in separate con
tainers or in the same container.

11. The reactor assembly according to any one of claims 7 -

10, wherein the containers for the treatment zones are
mounted outside the main box housing the reactor assembly.

12. The reactor assembly according to any one of claims 7 -

11, wherein means are provided for monitoring the individu
a l parts thereof, especially the pre-reformer system.

13. The reactor assembly according to claim 12, wherein

the monitoring of the pre-reformer system i s based on the
o deactivation plot to evaluate the deactivation rate of
the catalyst (s) .

14. The reactor assembly according to any one of claims 7 -

13, wherein the monitoring of gum formation in the pre-
reformer system i s based on measuring the pressure drop,
∆Ρ , from zone to zone in the system.

15. The reactor assembly according to any one of claims 7 -

14, wherein the pre-reformer comprises one or more beds
containing mixed catalysts.

16. The reactor assembly according to any one of claims 7 -

15, wherein the pre-reformer comprises two or more bed
types, each of which containing a different catalyst.
17. The reactor assembly according to any one of claims 8-

16, wherein the pre-reformer comprises one or more individ

ual beds, which are graduated.

18. The reactor assembly according to any one of claims 7-

17, wherein the pre-ref orming bed system i s provided with
replacement or bypass options based on a monitoring equip
ment for the guidance regarding when to effect replacement
of individual beds in the system.

19. The reactor assembly according to claim 18, wherein

the monitoring equipment i s connected to means for pressure
measurements and/or temperature measurements.

20. The reactor assembly according to any one of claims 7-

19, wherein the pre-ref orming bed system i s provided with
integrated means for hydrodesulf urization (HDS) , enabling

the fuel to b e converted to a more suitable feed for an in

ternal reforming fuel cell system.
A . CLASSIFICATION O F SUBJECT MATTER
H01M8/06 C01B3/00
H01M8/04 H01M8/12

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
H01M C01B

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

EP 0 673 074 Al (ROLLS ROYCE PLC [GB] ) 1-16,

20 September 1995 (1995-09-20) 18-20
col umn 12 , l i ne 1 - col umn 14, l i ne 1;
f i gure 1
col umn 8 , l i ne 4 1 - col umn 9 , l i ne 12

US 6 299 994 Bl (T0WLER GAVIN P [US] ET 1,3-5 ,

AL) 9 October 2001 (2001-10-09) 7-10, 16,
17 ,20
col umn 17 , l i ne 1 - col umn 18, l i ne 63 ;
f i gure 1
col umn 6 , l i nes 4-6

US 2006/090398 Al (KATI KAN EN I SAI P [US] 1,3-12 ,

ET AL) 4 May 2006 (2006-05-04) 15 , 16,
18,20
paragraphs [0029] - [0059] ; cl aim 66;
f i gures 1, 2 , 4

-/-
X| Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :

"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to be of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot be
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot be
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

1 1 September 2013 23/09/2013

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Brune, Markus
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2009/155649 Al (CUI JINGYU [US] ET AL) 1-5 ,

18 June 2009 (2009-06-18) 7-11 ,
20
paragraphs [0064] - [0175] ; f i gures 1-4

0 2005/094972 Al (VOLVO TECHNOLOGY CORP 1,3

[SE] ; LINDSTR0EM BAARD [SE] ; EKDUNGE PER
[SE] ) 13 October 2005 (2005-10-13)
page 3 , l i ne 15 - page 5 , l i ne 15 ; f i gure
1

W0 2005/081790 A2 (NU ELEMENT INC [US] ; 1,3

L0FFLER DANI EL G [US] )
9 September 2005 (2005-09-09)
page 2 , l i ne 18 - page 1 1 , l i ne 4 ; f i gure
1

W0 03/065488 Al (CERAMIC FUEL CELLS LTD 1-20

[AU] ; F0GER KARL [AU] )
7 August 2003 (2003-08-07)
the whol e document

DE 10 2006 023248 Al ( LURGI A G [DE] LURGI 1-20

GMBH [DE] ) 22 November 2007 (2007-11-22)
the whol e document
 Patent document Publication Patent family Publication
cited in search report date member(s) date

EP 0673074 Al 20-09-1995 CA 2142757 Al 20-08-1995

DE 69503167 Dl 06-08-1998
DE 69503167 T2 22-10-1998
EP 0673074 Al 20-09-1995
P 3845123 B2 15-11-2006
P H07272742 A 20-10-1995
US 5486428 A 23-01-1996
US 5595833 A 21-01-1997

US 6299994 Bl 09-10-2001 NONE

US 2006090398 Al 04-05-2006 CN 101287815 A 15 -10 -2008

EP 1819430 A2 22 -08 -2007
P 2008518870 A 05 -06 -2008
KR 20070085688 A 27 -08 -2007
US 2006090398 Al 04 -05 -2006
US 2009236265 Al 24 -09 -2009
US 2011192085 Al 1 1 -08 -2011
O 2006049795 A2 1 1 -05 -2006

US 2009155649 Al 18-06-2009 NONE

O 2005094972 Al 13 -10 -2005 AT 496677 T 15-02-2011

EP 1735081 Al 27-12-2006
US 2007034551 Al 15-02-2007
US 2009101544 Al 23-04-2009
WO 2005094972 Al 13-10-2005

wo 2005081790 A2 09 -09 -2005 US 2005229491 Al 20-10-2005

WO 2005081790 A2 09-09-2005

W0 03065488 Al 07-08-2003 AU 2003201391 B2 06-11-2008

CA 2474270 Al 07-08-2003
EP 1470605 Al 27-10-2004
JP 4782985 B2 28-09-2011
JP 2005516374 A 02-06-2005
US 2005074642 Al 07-04-2005
WO 03065488 Al 07-08-2003

DE 102006023248 Al 22-11-2007 CN 101448731 A 03-06-2009

DE 102006023248 Al 22-11-2007
EP 2021274 Al 11-02-2009
US 2009105356 Al 23-04-2009
WO 2007134727 Al 29-11-2007