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

(19) World Intellectual Property

Organization
International Bureau
(43) International Publication Date

4 October 2012 (04.10.2012)

IJ
~

11111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111111

(10) International Publication Number

WI PO I PCT

WO 2012/131318 A1

(81) Designated States (unless otherwise indicated, for every

kind of national protection available): AE, AG, AL, AM,
AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ,
International Application Number:
CA,CH,CL,CN,CO,CR,CU,CZ,DE,DK,DM,DO,
PCT/GB20 12/050493
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR,
International Filing Date:
KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,
6 March 2012 (06.03.2012)
MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
Filing Language:
English
OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD,
SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR,
Publication Language:
English
TT, TZ, VA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
Priority Data:
GB (84) Designated States (unless otherwise indicated, for every
1105131.5
28 March 2011 (28.03.2011)
kind of regional protection available): ARIPO (BW, GH,
Applicant (for all designated States except US): JOHNGM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
SON MATTHEY PUBLIC LIMITED COMPANY
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU,
[GB/GB]; 5th floor, 25 Farringdon Street, London EC4A
TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,
4AB (GB).
DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
Inventors; and
SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
Inventors/Applicants (for US only): FARNELL, Peter
GW, ML, MR, NE, SN, TD, TG).
William [GB/GB]; 36 Tanton Road, Stokesley, North
Yorkshire TS9 5HR (GB). FOWLES, Martin [GB/GB]; 9 Published:
Bridge Green, Danby, Nr. Whitby, North Yorkshire Y02l
with international search report (Art. 21(3))
2JQ (GB). SENGELOW, William Maurice [GB/GB]; 2
Brandon Close, Billingham, Cleveland TS23 2TH (GB).

(51) International Patent Classification:

COIB 3138 (2006.01)
COIB 3140 (2006.01)
(21)
(22)
(25)
(26)
(30)
(71)

(72)
(75)

--

(74) Agent: RIDLAND, John; Johnson Matthey Catalysts, Intellectual Property Department, PO Box I, Belasis Avenue,
Billingham Cleveland TS23 ILB (GB).

::: ------------------------------------------------------------------------------------------{54) Title: STEAM REFORMING

10

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(57) Abstract: A process for the steam reforming of hydrocarbons in an autothermal or secondary reformer is described comprising
(i) non-catalytically partially combusting a feedgas comprising a hydrocarbon with an oxygen-containing gas in the presence of
steam to form a partially oxidised hydrocarbon gas mixture at a temperature 2::1200C and (ii) passing the partially oxidised hydrocarbon gas mixture through a first particulate layer of steam reforming catalyst, a second particulate layer of steam reforming catalyst
and a third particulate layer of steam reforming catalyst, wherein the first layer comprises a catalytically active metal selected from
platinum, palladium, iridium, ruthenium or rhodium supported on a zirconia, and the second and third layers comprise nickel on a
refractory support selected from alumina, calcium aluminate, magnesium aluminate, titania, zirconia, magnesia or mixtures thereof,
wherein the second layer has a voidage 2::0.5 and a higher equivalent passage diameter than the third layer.

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Steam Reforming
This invention relates to a process and apparatus for the catalytic steam reforming of a partially
combusted hydrocarbon feedstock for the preparation of synthesis gas.

Steam reforming is widely practised and is used to produce hydrogen streams and synthesis
gas comprising hydrogen and carbon oxides for a number of processes such as ammonia and
methanol synthesis and the Fischer-Tropsch process. In order to obtain a synthesis gas more
suited to Fischer-Tropsch or other downstream processes, a primary or pre-reformed gas
containing methane is typically subjected to secondary or autothermal reforming in an adiabatic
refractory lined reformer by partially combusting the primary-reformed or pre-reformed gas in a
combustion zone using a suitable oxidant, e.g. air, oxygen or oxygen-enriched air using burner
apparatus mounted usually near the top of the reformer. The process of partially combusting
the primary-reformed or pre-reformed gas produces a partially oxidised gas mixture. The
refractory lining typically contains multiple layers and is designed to protect the pressure vessel
from the hot gases in the reformer and to provide insulation to minimise heat losses. One or
more layers of low thermal conductivity materials containing alumina may be used to provide
the thermal insulation. The hot face material is typically made from dense high purity alpha
alumina bricks that are chemically inert to the hot gases and resist physical attrition due the
high gas velocities employed. These blocks are cemented in place to prevent the hot process
gas contacting the more reactive insulating layers beneath.

The partial combustion reactions are exothermic and the partial oxidation increases the
temperature of the partially oxidised gas to between 1200 and 1500C. The partially oxidised
reformed gas is then passed from the combustion zone through a bed of a steam reforming
catalyst disposed below the burner apparatus, to bring the gas composition towards
equilibrium. Heat for the endothermic steam reforming reaction is supplied by the hot, partially
oxidised reformed gas. As the partially oxidised reformed gas contacts the steam reforming
catalyst it is cooled adiabatically by the endothermic steam reforming reaction to temperatures
in the range 900-1100C.

Typically the steam reforming catalyst in the secondary or autothermal reformer is a nickel
catalyst supported on an alpha alumina or a magnesium-, or calcium-aluminate support.

W02006/126018 discloses a process for the steam reforming of hydrocarbons in an

autothermal or secondary reformer, wherein in order to prevent volatilisation of the catalyst
support, the steam reforming catalyst bed comprises a first layer and a second layer, wherein
the oxidic support for the first layer is a zirconia. Preferably the catalytic activity of the first
layer is higher than the second layer so that the endothermic steam reforming reactions act to
reduce the gas temperature quickly and so prevent volatilisation of the catalyst. This may be

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2

achieved by using a more catalytically active metal in the first layer such as platinum,
palladium, iridium, ruthenium or rhodium.

Volatilisation of the dense alpha-alumina bricks used to line the adiabatic reformer, can occur
when the refractory lining in the vessel is new or when the dense alpha alumina bricks have
been replaced or repaired. This is a particular problem in the burner region and combustion
zone of the reformer where the gas temperatures are hottest. Volatilisation occurs until the
bricks and the cement used to hold the blocks together have aged in-situ. We have found
surprisingly that, where volatilised alumina is formed, it does not condense on the first zirconiasupported catalyst layer, despite the fact that it is cooled by the endothermic steam reforming
reactions, and is deposited instead in the second layer. In extreme cases, this can increase
the pressure drop though the bed of steam reforming catalyst causing the plant to reduce
throughput, and/or result in the non-uniform flow of gas through the catalyst bed resulting in
the apparent poor performance of the catalyst. Therefore we have devised an arrangement
that overcomes these problems.

Accordingly, the invention provides a process for the steam reforming of hydrocarbons in an
autothermal or secondary reformer comprising (i) non-catalytically partially com busting a
feedgas comprising a hydrocarbon with an oxygen-containing gas in the presence of steam to
form a partially oxidised hydrocarbon gas mixture at a temperature ~1200C and (ii) passing
the partially oxidised hydrocarbon gas mixture through a first particulate layer of steam
reforming catalyst, a second particulate layer of steam reforming catalyst and a third particulate
layer of steam reforming catalyst, wherein the first layer comprises a catalytically active metal
selected from platinum, palladium, iridium, ruthenium or rhodium supported on a zirconia, and
the second and third layers comprise nickel on a refractory support selected from alumina,
calcium aluminate, magnesium aluminate, titania, zirconia, magnesia or mixtures thereof,
wherein the second layer has a voidage

0.5 and a higher equivalent passage diameter than

the third layer.

The invention further provides a bed of steam reforming catalyst disposed below burner
apparatus in an autothermal or secondary reformer, wherein the bed comprises a first
particulate layer, a second particulate layer and a third particulate layer, wherein the first layer
comprises a catalytically active metal selected from platinum, palladium, iridium, ruthenium or
rhodium supported on a zirconia, and the second and third layers comprise nickel on a
refractory support selected from alumina, calcium aluminate, magnesium aluminate, titania,
zirconia, magnesia or mixtures thereof, and wherein the second layer has a voidage
a higher equivalent passage diameter than the third layer.

0.5 and

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3
In the process, the feed gas may comprise a desulphurised hydrocarbon feedstock, such as
methane or a natural gas, which may further comprise recycled gas streams from downstream
processes comprising one or more of methanol, hydrocarbons, carbon oxides or hydrogen, or
may be a pre-reformed or primary reformed gas stream comprising methane, steam, hydrogen
and carbon oxides. The latter are preferable as it may be desirable to ensure that the feed to
the secondary reformer or autothermal reformer contains no hydrocarbons higher than
methane and also contains a significant amount of hydrogen, as these factors reduce the risk
of carbon or soot formation above or on the steam reforming catalyst.

The oxygen containing gas may be substantially pure oxygen, air or an oxygen enriched air.
The oxygen:carbon molar ratio may be in the range 0.4 to 0.7:1. Steam is preferably present at
a steam:carbon ratio between 0.5 and 3.5. Steam may be provided by adding it directly to the
combustion zone or by mixing, either with the feedgas or the oxygen-containing gas.
Alternatively, if the feedgas is a pre- or primary-reformed gas, no additional steam may be
necessary. Furthermore, if the feedgas contains hydrogen, its combustion with oxygen will
generate steam under the reaction conditions. The hydrocarbon in the feedgas is noncatalytically partially com busted by the oxygen in the oxygen-containing gas in the combustion
zone of a secondary or autothermal reformer. The combustion zone is generally formed
beneath a burner disposed near the top of the reformer to which the feed gas and oxygencontaining gas are fed.

The partially oxidised hydrocarbon/steam mixture then passes from the combustion zone to the
surface of the first layer of steam reforming catalyst at a temperature ~1200C and preferably in
the range 1200-1500C. When the partially oxidised feedgas/steam mixture, e.g. a partially
combusted pre- or primary reformed gas, contacts the steam reforming catalyst, the steam
reforming reaction, which is endothermic, cools the gas and the surface of the catalyst. The
surface temperature of the catalyst may therefore, depending upon the conditions and activity
of the catalyst, be in the range about 900-1400C. In particular, we have found alumina or
metal aluminate volatilisation to occur when the catalyst temperature is above about 1150C,
particularly about 1200C. Thus, preferably the first layer reduces the catalyst temperature
below about 1200C, more preferably below about 1100C.

The pressures at which the process may be operated are preferably

~20

bar abs, more

preferably in the range 20 to 80 bar abs. The gas-hourly space velocity in the catalyst layers
may be ~5000h- 1 , preferably 5000 to 30000h- 1 , more preferably 5000 to 20000h- 1 .

In the present invention, the first layer catalyst support is a zirconia. Preferred zirconia
supports are stabilised zirconias, such as magnesia-, calcia-, lanthana-, yttria- or ceriastabilised zirconias, which are most preferably in the cubic form. Such zirconias are known and

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are commercially available. Yttria-stabilised cubic zirconia is most preferred, e.g. a 16% wt
yttria-stabilised cubic zirconia. Typically such stabilised zirconias have been fired to
temperatures above 1200C. We have found zirconia-containing supports to have lower
volatility than supports comprising alumina or magnesium- or calcium-aluminate and so the
presence in the first layer of alumina or magnesium- or calcium-aluminate is undesirable.

The catalytically active metal in the first layer of steam reforming catalyst may platinum,
palladium, iridium, ruthenium or rhodium, preferably platinum and/or rhodium. These metals
have a higher catalytic activity/g and greater stability than the conventional nickel steam
reforming catalysts, which has the further advantage or reducing catalyst volatilisation. By
increasing the catalytic activity of the first layer, the endothermic steam reforming reactions
take place to a greater extent and thereby act to cool the gas stream passing through the bed
more rapidly than in the case where the layer of increased activity is absent. Rhodium is
particularly preferred as it has a lower vapour pressure than nickel under typical reaction
conditions. Suitably active rhodium catalysts comprise 0.01-1.00%, preferably 0.05 to 0.5%,
more preferably 0.1 to 0.25% Rh by weight. A particularly preferred first layer catalyst therefore
consists of a rhodium impregnated zirconia catalyst, particularly a 0.05 to 0.5%wt rhodiumimpregnated stabilised zirconia.

The partially reformed gas mixture passes from the first layer to the second and third layers
respectively. The second and third layers comprise a nickel catalyst on a suitable refractory
support. The refractory catalyst support for the second layer preferably comprises alumina,
calcium aluminate, magnesium aluminate, titania, zirconia or magnesia or mixtures thereof.
More preferably, the second layer catalyst and third layer catalyst comprise nickel on alumina,
magnesium aluminate or calcium aluminate.

Steam reforming catalysts may be made using a variety of methods. Impregnation methods
are particularly suitable and are well known to those skilled in the art of catalyst manufacture.
For example, rhodium may be provided in the first layer steam reforming catalyst by
impregnation of the zirconia support with a solution of a suitable rhodium compound, followed
by heating in air to convert the compound to rhodium oxide. If desired, the rhodium oxide may
then be reduced to elemental form by treatment with a reducing gas such as hydrogen at
elevated temperature, although it is generally more convenient to install the catalyst in the unreduced oxidic form and perform the reduction immediately prior to use in-situ by reaction with
a reducing gas (hydrogen and/or carbon monoxide). For example, a rhodium catalyst may be
prepared by impregnating a stabilised cubic zirconia with an aqueous solution of rhodium
nitrate, if necessary separating the impregnated material from the solution, drying and calcining
to 400-500C. The rhodium oxide, Rh 2 0 3 , is subsequently reduced in-situ. In a preferred
embodiment, the rhodium is provided on the support as a so-called "eggshell" catalyst in which

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5
the rhodium is concentrated in the surface layers of the catalyst support rather than being
distributed evenly throughout the support. This provides a more efficient use of the rhodium,
which is relatively expensive, compared to e.g. nickel.

Nickel catalysts may similarly be formed by impregnation of the refractory oxide support with
nickel acetate or nickel nitrate, followed by calcination, or by precipitation of nickel compounds
by combining a solution of a nickel salt such as nickel nitrate with a base, followed by washing,
drying, and calcining. Again prior to use the nickel may be reduced with a reducing gas
stream.

Whereas impregnation of soluble salts is a particularly suitable method for preparing the
catalysts, other techniques whereby sols or suspensions of catalytic metals are applied to the
support material may also be used.

The first, second and third layer reforming catalysts are particulate, i.e. in the form of shaped
units such as pellets, rings or extrudates, which may be lobed or fluted and/or which may
contain one or more through holes. Such catalysts are commercially available or may be made
using conventional techniques.

In the present invention, the second layer has a voidage

0.5,

preferably~

0.55 and the

equivalent passage diameter (Dep) is higher in the second layer, in which the volatilised alumina
condenses, than in the third. In this way the condensation of volatilised alumina will have a
reduced effect on the pressure drop of the catalyst bed and is less likely to result in nonuniform flow through the bed. However, it is still desirable that the second layer catalyst activity
is sufficient, and this may be achieved by using catalysts with a suitable geometric surface area
(GSA).

Voidage (s) is a dimensionless number related to the interstitial "empty" volume between and
within the catalyst particles present in the layers. Voidage is described, for example, in The
Catalyst Handbook,

2nd

Edition, Manson Publishing, 1989, pages 101-5. The shape of the

catalyst particle can be used to determine the voidage of the catalyst layer- generally the more
eccentric the shape, the greater the voidage. Thus higher voidages may be achieved using
particles with an aspect ratio, i.e. a length/diameter value, other than 1.0. Solid cylinders
generally have a low voidage, typically <0.4. Voidage may also be increased by providing the
catalyst particles with one or more through holes, preferably 1 to 10 through holes. Whereas
rings with adequate strength can provide increased voidage, their GSA may not be suitable.
Accordingly preferred catalysts have 2-10 through holes. Voidage may also be increased by
providing the catalyst particles with lobes or flutes. Particularly preferred catalyst particles are

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6
4 to 10 holed cylindrical pellets, optionally with lobes or flutes arranged around their periphery,
and which may be domed or flat ended.

The second layer may have the same or different voidage to the first or third layers. Preferably
the voidage in the second layer will be the same or higher than that in the third layer. The
voidage of the second layer may also be the same or higher than that of the first layer. A high
voidage of the second layer allows the volatilised alumina to be captured without adversely
increasing the pressure drop through the bed.
The equivalent passage diameter, or hydraulic diameter,

is given in the Chemical

Dep,

Engineer's Handbook, 5 h Edition, Table 5-11 as 4 x RH, where RH is the area of the fluid stream
cross-section/wetted perimeter. In a particulate catalyst bed
2

as 4 x voidage/geometric surface area in m /m

i.e.

Dep

Dep

(in metres) may be expressed

= 4s/GSA.

The Geometric Surface Area (GSA) may be calculated from the dimensions of the catalyst
particles using known methods. For example, GSA may be calculated for ring or multi-hole
cylindrical catalysts using the expression, GSA= S.(1-s)N, where Sis the surface area of the
catalyst, s is the voidage and V is the volume of the catalyst particle.
2

S = rc.L.(D 0 +(Nh.D;))+0.5.rc.(D 0 -(Nh.D;

))

and V = 0.25.rc.L.(D 0 -(Nh.D;

where Lis the length of

the catalyst particle, Do is the outside diameter, D; is the inside diameter, and Nh is the number
of holes.

The second layer has a higher equivalent passage diameter than third layer. It may also have
a higher equivalent passage diameter than the first layer. This may be achieved by using
larger particles of the same voidage (as a result of their lower GSA) or by increasing the
voidage of the catalyst particles in the second layer as described above.

The equivalent passage diameter of the second layer is

~

7mm, most

preferably~

8mm,

especially~

preferably~

6mm, more preferably

9mm. A suitable upper limit for the equivalent

passage diameter in the second layer may be 15mm. The equivalent passage diameter in the
first or third layers is preferably smaller by 1 or more millimetres, i.e. the difference between the
Dep

of the second and first or third layers is preferably

1mm, with a minimum value of the

Dep

in the first and third layers preferably of 2 mm.

The second layer therefore preferably has a combination of sufficient volume to capture the
volatilised alumina without adversely affecting the pressure drop or flow distribution and
sufficient GSA to catalyse the reaction to further reduce gas temperature thereby promoting
complete condensation of the volatilised alumina in the second layer and at the same time
contributing towards the approach to equilibrium for the reformed gas. This is achieved by
selecting catalyst particles with the appropriate voidage and equivalent passage diameter. The

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7
geometric surface area of the second layer is preferably ~150m /m , more preferably
2

~200m /m , up to about 350m /m

2

The GSA of the third layer is preferably higher than that of

the second layer so that the reacting gasses may be brought towards equilibrium in the
autothermal reformer. The geometric surface area of the first layer may also be higher than
that of the second layer for the same reason. The GSA of the first layer and the third layer is
2

preferably ~300m /m , more preferably ~400m /m , with an upper limit preferably about
2

650m /m

Preferably, there is a difference in GSA between the first or third layers and the
2

second layer of at least 50 m /m

In a preferred embodiment, the bed of steam reforming catalyst comprises a first layer
comprising 0.05 to 0.5% wt Rh on a stabilised zirconia, in the form of multi-holed cylindrical
pellets, which may be lobed or fluted, with a voidage

0.5, over a second layer comprising 5-

20% wt Ni on alumina in the form of rings or multi-holed cylindrical pellets having voidage
and a

Dep ~

0.5

6mm, over a third layer comprising a 5- 20% wt Ni on alumina in the form of multi-

holed pellets, which may be lobed or fluted, with a voidage

0.5 and

Dep ~

1 mm smaller than

that of the second layer.

The thickness of the bed of the steam reforming catalyst will depend upon the feed rate, the
activity of the catalytically active metals, the conditions under which it is operated and whether
the feedgas is a hydrocarbon/steam mixture or a pre- or primary-reformed gas. The thickness
of the bed of steam reforming catalyst may be in the range 1-10 metres, preferably 2-5 metres
with the first and second layers each preferably comprising between 3 and 25%, most
preferably 5 and 15% of the thickness of the bed.

If desired, a layer of zirconia balls, pellets or perforate tiles may be placed on top of the first
layer of reforming catalyst to protect the surface of the steam reforming catalyst from
irregularities in the combusting gas flow. A benefit of providing this layer is to prevent
disturbance of the surface of the particulate catalyst bed.

It will be understood by those skilled in the art that it may be useful to graduate the activity of
the steam reforming catalyst through the bed. Therefore the third layer may comprise two or
more successive layers of a steam reforming catalyst, the fourth or further layers having a
higher catalytic activity than that preceding it.

The invention will now be further described by reference to the figures in which;
Figure 1 is depiction of an autothermal reformer containing a catalyst bed according to one
embodiment of the invention.

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In Figure 1 and autothermal reformer vessel 1 comprises an upper section comprising a burner
tube 10 to which an oxygen-containing gas may be fed and an inlet 12 to which a feedgas
comprising a hydrocarbon may be fed. The hydrocarbon-containing feedgas passes from the
inlet and though a perforate diffuser 14 to a lower combustion zone 16 to which the burner tube
10 extends. The walls of the vessel are lined with multi-layer alumina-containing refractory
liner 18. The oxygen-containing gas from the burner tube mixes with the hydrocarboncontaining feedgas and partially combusts in the combustion zone 16. The hot, partially
oxidised gas then passes through a layer of perforate refractory oxide target tiles 20 and a
catalyst bed 22, 24, 26 disposed beneath the combustion zone 16. The catalyst bed comprises
three layers 22, 24, and 26. The first layer 22 comprises a catalytically active metal selected
from platinum, palladium, iridium, ruthenium or rhodium supported on a zirconia, and the
second 24 and third 26 layers comprise nickel on a refractory support selected from the group
consisting of alumina, calcium aluminate, magnesium aluminate, titania, zirconia, magnesia or
mixtures thereof. The second layer has a voidage

~0.5

and a higher equivalent passage

diameter than the third layer. The partially oxidised gas is steam reformed by the steam
reforming catalysts 22, 24, 26 and the resulting gas mixture brought towards equilibrium as it
passes down through the bed. The catalyst bed is supported within the vessel by refractory
oxide units 28, such as alumina spheres, which allow the reformed gas to pass from the
catalyst bed to a perforate end-member 30 and thence from the vessel via a reformed gas
outlet 32.

The alumina volatilised from refractory liner 18 passes though the tiles 20 (which are at the
same temperature as the hot gasses in the combustion zone), and surprisingly also through the
first layer 22 despite the cooling effect of the endothermic stream reforming reactions. The
volatilised alumina condenses in the second layer. Because the second layer has a voidage
~0.5

and a higher equivalent passage diameter, the deposited alumina does not negatively

affect the pressure drop through the bed compared to the case where the second layer is
absent.

In a specific embodiment an autothermal reformer was loaded with a catalyst bed comprising a
0.1-0.3 m thick layer of perforate zirconia tiles and lumps on top of a 0.1-0.2 m thick first layer
of a Rh/Zr0 2 steam reforming catalyst (KATALCOJM TM 89-6GQ) on a 0.2-0.3m thick second
layer of a large diameter 4-holed cylindrical Ni/AI 20 3 steam reforming catalyst (KATALCOJM 238E) on a 1-2m thick third layer of a smaller diameter 4-hole quadralobe Ni/AI 2 0 3 steam
reforming catalyst (KATALCOJM 28-40).

In an alternative specific embodiment, an autothermal reformer was loaded with a catalyst bed
comprising a layer of perforate zirconia tiles on top of a 0.1-0.3 m thick first layer of a Rh/Zr0 2
steam reforming catalyst (KATALCOJMTM 89-6GQ or KATALCOJMTM 89-6EQ) on a 0.2-0.3m

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9
thick second layer of a large diameter 4-holed cylindrical Ni/AI 20 3 steam reforming catalyst
(KATALCOJM 23-8E) on a 2-3m thick third layer of a smaller diameter 4-holed cylindrical
Ni/AI 20 3 steam reforming catalyst (KATALCOJM 28-4GQ).

In both cases, the catalysts are commercially available from Johnson Matthey Catalysts.

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1.

A process for the steam reforming of hydrocarbons in an autothermal or secondary

reformer comprising (i) non-catalytically partially com busting a feedgas comprising a
hydrocarbon with an oxygen-containing gas in the presence of steam to form a partially
oxidised hydrocarbon gas mixture at a temperature ~1200C and (ii) passing the
partially oxidised hydrocarbon gas mixture through a first particulate layer of steam
reforming catalyst, a second particulate layer of steam reforming catalyst and a third
particulate layer of steam reforming catalyst, wherein the first layer comprises a
catalytically active metal selected from platinum, palladium, iridium, ruthenium or
rhodium supported on a zirconia, and the second and third layers comprise nickel on a
refractory support selected from alumina, calcium aluminate, magnesium aluminate,
titania, zirconia, magnesia or mixtures thereof, wherein the second layer has a voidage
~

2.

0.5 and a higher equivalent passage diameter than the third layer.

A process according to claim 1 wherein the catalytically active metal in the first layer of
steam reforming catalyst comprises rhodium and/or platinum, preferably rhodium.

3.

A process according to claim 1 or claim 2 wherein the refractory support for the second
layer is selected from the group consisting of alumina, calcium-aluminate, magnesiumaluminate or mixtures thereof.

4.

A process according to any one of claims 1 to 3 wherein the refractory support for the
third layer is selected from the group consisting of alumina, calcium-aluminate,
magnesium-aluminate or mixtures thereof.

5.

A process according to any one of claims 1 to 4 wherein the equivalent passage

diameter of the second layer
especially~

6.

6mm,

preferably~

7mm, more

preferably~

8mm,

9mm.

A process according to any one of claims 1 to 5 wherein the second layer has a
voidage

7.

is~

0.55.

A process according to any one of claims 1 to 6 wherein the third layer has a geometric
surface area higher than that of the second layer.

8.

A process according to any one of claims 1 to 7 wherein the third layer has a geometric
surface area~ 300m /m
2

preferably~ 400m /m
2

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9.

A process according to any one of claims 1 to 8 wherein a layer of zirconia balls,

pellets or tiles is placed on top of the first layer of reforming catalyst.

10. A process according to any one of claims 1 to 9 wherein the third layer comprises two
or more successive layers of a steam reforming catalyst, the fourth or further layers
having a higher catalytic activity than that preceding it.

11. A bed of steam reforming catalyst disposed below burner apparatus in an autothermal
or secondary reformer, wherein the bed comprises a first particulate layer, a second
particulate layer and a third particulate layer, each layer comprising a catalytically
active metal and an oxidic support wherein the first layer comprises a catalytically
active metal selected from platinum, palladium, iridium, ruthenium or rhodium
supported on a zirconia, the second and third layers comprise nickel on a refractory
support selected from alumina, calcium aluminate, magnesium aluminate, titania,
zirconia, magnesia or mixtures thereof, and wherein the second layer has a voidage
~0.5

and a higher equivalent passage diameter than the third layer.

12. A catalyst bed according to claim 11 wherein the first layer comprises rhodium on a
zirconia and the second and third layers comprises nickel on an alumina or
magnesium-aluminate or calcium-aluminate support.

13. A catalyst bed according to claim 11 or claim 12 wherein the first and second layers are
each between 5 and 25% of the thickness of the bed.

14. A catalyst bed according to any one of claims 11 to 13 wherein an inert layer of zirconia
balls, pellets or tiles is placed on top of the first layer of reforming catalyst.
15. A catalyst bed according to any one of claims 11 to 14 wherein the third layer
comprises two or more successive layers of a steam reforming catalyst, the fourth or
further layers having a higher catalytic activity than that preceding it.

wo 2012/131318

PCT/GB2012/050493

1/1

10

12
u---....L.----L...---u.-- 14

18

20

t:~~~;::t-22
24

26

28

Figure 1

INTERNATIONAL SEARCH REPORT

International application No

PCT/GB2012/050493
A. CLASSIFICATION OF SUBJECT MATTER

INV.
ADD.

C01B3/38

C01B3/40

According to International Patent Classification (I PC) or to both national classification and IPC
B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)

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, COMPENDEX

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category

Citation of document, with indication, where appropriate, of the relevant passages

wo

X,P

2011/113611 A2 (TOPSOE HALDOR AS [DK];

SKJOETH-RASMUSSEN MARTIN SKOV [DK];
MORALES CAN)
22 September 2011 (2011-09-22)
the whole document

1-15

wo

1-15

-----

2006/126018 A1 (JOHNSON MATTHEY PLC

[GB]; FARNELL PETER WILLIAM [GB]; FOWLES
MARTIN [G) 30 November 2006 (2006-11-30)
cited in the application
page 5, last paragraph
claims 1,2,5,6,7,10

-----

[]]

Further documents are listed in the continuation of Box C.

Special categories of cited documents :

"A" document defining the general state of the art which is not considered
to be of particular relevance
"E" earlier application or patent but published on or after the international
filing date
"L" document which may throw doubts on priority claim(s) or which is
cited to establish the publication date of another citation or other
special reason (as spec~ied)
"0" document referring to an oral disclosure, use, exhibition or other
means

"P" document published prior to the international filing date but later than
the priority date claimed
Date of the actual completion of the international search

30 May 2012

Relevant to claim No.

Name and mailing address of the ISAI

European Patent Office, P.B. 5818 Patentlaan 2
NL- 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016

-!--

lRJ

See patent family annex.

"T" later document published after the international filing date or priority
date and not in conflict with the application but cited to understand
the principle or theory underlying the invention

"X" document of particular relevance; the claimed invention cannot be

considered novel or cannot be considered to involve an inventive
step when the document is taken alone

"Y" document of particular relevance; the claimed invention cannot be

considered to involve an inventive step when the document is
combined with one or more other such documents, such combination
being obvious to a person skilled in the art

"&" document member of the same patent family

Date of mailing of the international search report

19/06/2012
Authorized officer

Harf-Bapin, E

Form PCT/ISA/21 0 (second sheet) (April 2005)

page 1 of 2

INTERNATIONAL SEARCH REPORT

International application No

PCT/GB2012/050493
C(Continuation).
Category

DOCUMENTS CONSIDERED TO BE RELEVANT

Citation of document, with indication, where appropriate, of the relevant passages

Relevant to claim No.

F. BENYAHIA ET AL: "Enhanced Voidage

Correlations for Packed Beds of Various
Particle Shapes and Sizes".
PARTICULATE SCIENCE AND TECHNOLOGY.
vol. 23. no. 2. 1 April 2005 (2005-04-01).
pages 169-177. XP55028273.
ISSN: 0272-6351. DOl:
10.1080/02726350590922242
the whole document

1-15

US 2003/083198 A1 (XU BANG CHEN [US] ET

AL) 1 May 2003 (2003-05-01)
the whole document

1-15

2
Form PCT/ISA/21 0 (continuation of second sheet) (April 2005)

page 2 of 2

INTERNATIONAL SEARCH REPORT

International application No

Information on patent family members

Patent document
cited in search report

Publication
date

PCT/GB2012/050493
Patent family
member(s)

Publication
date

wo 2011113611 A2 22-09-2011 NONE

----------------------------------------------------------------------wo 2006126018 A1 30-11-2006 AU 2006250933 A1
30-11-2006
BR
CN
EA
EP
NZ

us

PI0611199
101180237
200702597
1883604
563419
2008197323
2006126018
200709562

A2
A
A1
A1
A
A1
A1
A

24-08-2010
14-05-2008
28-04-2008
06-02-2008
30-09-2010
21-08-2008
30-11-2006
29-10-2008

2003083198 A1
2005181939 A1

01-05-2003
18-08-2005

wo
ZA
-----------------------------------------------------------------------

us 2003083198

A1

01-05-2003

us
us

-----------------------------------------------------------------------

Form PCT/ISA/21 0 (pa1en1 family annex) (April2005)