U.S. patent application number 10/188307 was filed with the patent office on 2003-01-30 for reactor for catalytic conversion of a fuel.
This patent application is currently assigned to Ballard Power Systems Inc.. Invention is credited to Boneberg, Stefan, Schussler, Martin.
Application Number | 20030021739 10/188307 |
Document ID | / |
Family ID | 7690756 |
Filed Date | 2003-01-30 |
United States Patent
Application |
20030021739 |
Kind Code |
A1 |
Boneberg, Stefan ; et
al. |
January 30, 2003 |
Reactor for catalytic conversion of a fuel
Abstract
A reactor is provided for the catalytic conversion of a mixture
of a reactants, such as fuel, into at least one reaction product,
the reactor having a reaction chamber containing at least one
catalytically active substance for the conversion. The reactor
chamber further has a reaction area that at start-up is not yet
reactive at ambient temperature, and an ignition area that is
already capable of ignition at ambient temperature. Ignition area
is in only partial contact with reaction area, and the ignition
area is porous and contains one or more noble metals. The thermal
contact between the two different areas is such that the heat
output dissipated from the ignition area at ambient temperature is
less than the heat output generated in this area.
Inventors: |
Boneberg, Stefan; (Beuren,
DE) ; Schussler, Martin; (Ulm, DE) |
Correspondence
Address: |
SEED INTELLECTUAL PROPERTY LAW GROUP PLLC
701 FIFTH AVE
SUITE 6300
SEATTLE
WA
98104-7092
US
|
Assignee: |
Ballard Power Systems Inc.
Kirchheim - Nabern
DE
|
Family ID: |
7690756 |
Appl. No.: |
10/188307 |
Filed: |
July 1, 2002 |
Current U.S.
Class: |
422/173 |
Current CPC
Class: |
B01J 8/025 20130101;
C01B 2203/0244 20130101; C01B 2203/1604 20130101; C01B 3/386
20130101; C01B 2203/1023 20130101; B01J 8/0221 20130101; B01J
2208/00415 20130101; C01B 2203/047 20130101; B01J 2208/00398
20130101; B01J 2208/025 20130101; C01B 2203/1035 20130101; B01J
8/0285 20130101; C01B 3/583 20130101; C01B 2203/044 20130101; C01B
3/382 20130101; C01B 2203/0261 20130101; Y02P 20/52 20151101; B01J
35/0006 20130101 |
Class at
Publication: |
422/173 |
International
Class: |
F01N 003/10 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 5, 2001 |
DE |
10132673.4 |
Claims
1. A reactor for the catalytic conversion of a mixture of reactants
into at least one reaction product, the reactor having a reactor
chamber with at least one inlet opening for the reactants and at
least one outlet opening for the one or more reaction products, and
at least one catalytically active substance for the conversion of
the mixture of reactants into the at least one reaction product,
the reactor chamber comprising a reaction area that at start-up is
not yet reactive at ambient temperature and an ignition area which
is already capable of ignition at ambient temperature, wherein the
ignition area is only in partial contact with the reaction area and
the ignition area is porous and contains one or more noble metals,
wherein the thermal contact between the reaction area and the
ignition area is such that the heat output dissipated from the
ignition area at ambient temperature is less than the heat output
generated in the ignition area.
2. The reactor of claim 1 wherein the ignition area is ignitable at
temperatures down to -20.degree. C.
3. The reactor of claim 1 wherein the ignition area has a high
concentration of catalytically active substance in relation to its
macroscopic external surface.
4. The reactor of claim 1 wherein the ignition area is arranged
essentially downstream of the reaction area.
5. The reactor of claim 1 wherein the catalytically active
substance of the ignition area has a particle size or particle size
distribution ranging from 10 and 1000 .mu.m.
6. The reactor of claim 1 wherein the ignition area is applied in a
layer thickness of 10-1000 .mu.m.
7. The reactor of claim 1 wherein the ignition area is electrically
heatable or ignitable.
8. A method for the catalytic conversion of a mixture of reactants
into at least one reaction product, comprising introducing the
mixture of reactants into the at least one inlet opening input of
the reactor of claim 1.
9. The method of claim 8 wherein the conversion comprises partial
oxidation of the mixture of reactants.
10. The method of claim 8 wherein the conversion comprises
autothermal reformation of the mixture of reactants.
11. The method of claim 8 wherein the conversion comprises
selective CO oxidation.
12. The method of claim 8 wherein reactor is a catalytic
burner.
13. The method of claim 8 wherein the reactor is a catalytically
heated heat exchanger.
14. The method of claim 8 wherein the reactor is used in
conjunction with a fuel cell.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority under 35 U.S.C. .sctn.119
to German Application No. 10132673.4, filed Jul. 5, 2001, which
priority application is incorporated herein by reference in its
entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention pertains to a reactor for catalytic conversion
of a mixture of reactants, as well as to the operation thereof.
[0004] 2. Description of the Related Art
[0005] Reactors for catalytic conversion are normally started in
their entirety or have precombustors that introduce the heat
convectively. Between the precombustor and the actual reactor,
additional metering may be provided to allow combustible mixtures
in normal operation to be created only downstream of the
precombustor. EP 0 757 968 A1 describes a device for the generation
of hydrogen in which the upstream combustor stages are integrated
into the reactor such that no intermediate metering of a
combustible mixture is possible. This was implemented by a mixture
of powder at the input of a bed-type reactor. Even in reactors with
integrated precombustors, however, the heating of the entire
reactor takes place essentially in a convective manner.
[0006] For cold-starting reactors with catalyst-supporting
structures of high heat capacity, a rapid and reliable cold start
is highly desirable. This applies in particular to reactors with a
plate heat exchanger construction. The start-up must also be
reliable under conditions of high humidity and freezing
temperatures.
[0007] If a preliminary stage is used for cold-starting, high
temperatures are necessary for heat input. If a combustible mixture
is fed to the reactor (e.g., a CO oxidizer) even in normal
operation, the oxidation of the fuel already takes place in the
preliminary stage, at least in part, and results in a preliminary
stage running at a high temperature during normal operation.
Because of the unselective oxidation taking place at these
temperatures, undesired reaction products are also obtained. The
high temperatures are detrimental to the service life of the
reactor, not only in respect to the high temperatures of the gas
generated, which must subsequently be cooled, but also in respect
to high material stress and premature catalyst aging. If one wishes
to avoid premature oxidation of the fuel, the combustible mixture
must be fed in only between the precombustor and the reactor. This
makes an additional metering point, including a mixer, necessary
and thus leads to a more elaborate and expensive device.
[0008] Accordingly, there remains a need for improved reactors for
catalytic conversion of a fuel, particularly reactors with improved
cold-start and/or rapid response behavior under conditions of high
humidity and freezing temperatures. The present invention addresses
some or all of these needs and provides further related
advantages.
BRIEF SUMMARY OF THE INVENTION
[0009] In brief, this invention obviates the need for a preliminary
stage or a precombustor upstream of the reactor and/or additional
metering points for the fuel mixture between precombustor and
reactor.
[0010] In one embodiment, a reactor for the catalytic conversion of
a mixture of reactants into at least one reaction product is
provided, wherein the reactor contains a reactor chamber with at
least one inlet opening for the reactants and at least one outlet
opening for one or more reaction products, and at least one
catalytically active substance for the conversion. The reactor
chamber has two different areas, a reaction area that at start-up
is not yet reactive at ambient temperature, and an ignition area
which is already capable of ignition at ambient temperature,
wherein the ignition area is only in partial contact with the
reaction area and the ignition area is porous and contains one or
more noble metals. The thermal contact between the two different
areas is such that the heat output dissipated from the ignition
area at ambient temperature is less than the heat output generated
in this area.
[0011] In a more specific embodiment, and for optimal starting
behavior of the reactor, the ignition area has a high concentration
of catalytically active substance or of catalytically active
catalyst surface in relation to its macroscopic external surface.
This can be achieved, for instance, by greater layer thicknesses of
the catalytically active substance of roughly 10-1000 .mu.m,
preferably 50-300 .mu.m in this area, or by large particle
diameters of the catalytically active substance.
[0012] In further embodiments, a low flow velocity is employed in
the ignition area during the starting phase, so that a reduced
amount of heat is emitted to the circulating gas. In still another
embodiment, the amount of catalyst or catalytically active catalyst
surface in the reaction area of the reactor is large in relation to
the overall mass or overall heat capacity of the reaction area.
Advantageously, the ignition area of the reactor according to the
invention is already capable of ignition at temperatures down to
-40.degree. C., and typically at temperatures down to -20.degree.
C.
[0013] These and other aspects will be evident upon reference to
the attached figures and following detailed description.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0014] FIG. 1 is a representative arrangement of reaction area 1
and ignition area 2.
[0015] FIGS. 2a and 2b are further representative arrangements of
reaction area 1 and ignition area 2.
[0016] FIG. 3 illustrates the dependency of the heat output
generated at and dissipated from the catalyst on catalyst
temperature.
DETAILED DESCRIPTION OF THE INVENTION
[0017] As noted above, this invention eliminates the need for a
preliminary stage or a precombustor upstream of the reactor and/or
additional metering points for the fuel mixture between
precombustor and reactor. In the practice of this invention, a
reactor for the catalytic conversion of a mixture of reactants into
at least one reaction product is provided. The reactor contains a
reactor chamber with at least one inlet opening for the reactants
and at least one outlet opening for one or more reaction products.
The reactor chamber also contains at least one catalytically active
substance for the conversion.
[0018] Referring to FIG. 1, the reactor chamber has two different
areas, reaction area 1 that is not yet reactive at ambient
temperature, and ignition area 2 which is already capable of
ignition at ambient temperature, wherein ignition area 2 is only in
partial contact with reaction area 1 and ignition area 2 is porous
and contains one or more noble metals. The thermal contact between
the two different areas is such that the heat output dissipated
from the ignition area at ambient temperature is less than the heat
output generated in this area.
[0019] Starting of the reactor is initially accomplished by rapid
catalytic heating (ignition) of the ignition area, which is
optimized for this purpose. In this context, ignition means that
the reaction rate at the starting temperature is sufficiently high
that the removed heat output is not enough to keep the area in the
range of the starting temperature. The reaction rate then also
increases exponentially with the temperature and increases the heat
output. By solid-state thermal conduction from this thermally
poorly coupled ignition area 2, heat is then conducted by way of
existing thermal bridges into reaction area 1. Additionally,
reaction area 1 is gradually heated up by means of catalytic
oxidation by the catalyst located therein. Only at considerably
higher temperatures, roughly temperatures around 200-300.degree.
C., when material transport limits the reaction rate, does a
stationary state arise. Ignition area 2 can optionally be
electrically heated or ignited at the start.
[0020] The resulting equilibrium temperatures are highly dependent
on the thermal coupling between the reaction area and ignition
area. Referring to FIG. 3, curve 1 shows a typical
temperature-dependency of the reaction rate, which first increases
exponentially and is then limited by material transport at higher
temperatures. On the other hand, curve 2 shows that with good
thermal coupling to the environment, the stationary temperature of
the catalyst is only slightly higher than the ambient temperature
(i.e., even a slight temperature increase results in greater energy
emission). A cold start is therefore not possible, due to the very
good thermal coupling. In contrast, if heat transfer to the
environment is poor, as shown in curve 3, then a stationary
operating point arises only at a temperature that is considerably
elevated with respect to the environment. That means that ignition
results. (The heat transfer coefficients labeled .beta..sub.1 and
.beta..sub.2 in FIG. 3 follow the relation:
.beta..sub.2>.beta..sub.1.) In a representative embodiment, and
again referring to FIG. 1, ignition area 2 comprises a porous noble
metal-containing particle with a particle size or particle size
distribution between roughly 10 and 1000 .mu.m, and typically
between roughly 50 and 300 .mu.m. The noble metal-containing
particle, which typically contains platinum or palladium, may be on
a substrate. It is well know to one skilled in this field that
there are a number of substrate materials suitable for catalysts,
including ceramics, carbon, metal, plastic, and the like. For
example, porous solids, on the surface of which catalytically
active material can be deposited, are particularly suited. Ceramic
materials such Al.sub.2O.sub.3, zeolites, SiO.sub.2, ZrO.sub.2,
CeO.sub.2 and/or mixtures thereof are also used as substrate
materials, with Al.sub.2O.sub.3 having been found to be
particularly suitable. The porosity of the catalyst particle has
the effect that the reaction can run in the inner areas of the
catalyst particles both in the starting phase and in normal
operation of a reactor.
[0021] As shown in FIG. 1, the noble metal-containing porous
particle is only in partial contact with reaction area 1, these
contacts to reaction area 1 representing thermal bridges;
otherwise, ignition area 2 is weakly coupled thermally to reaction
area 1. The microscopic catalyst surface in the particle (also
called internal surface O.sub.1), the reaction rate at a given
temperature (r(T)) and the reaction enthalpy (H) determine, among
other things, the heat generated at start-up (P.sub.generated) at
ambient temperature according to the following equation:
P.sub.generated=O.sub.1.times.r(T).times.H
[0022] The number and extent of the contact points, the diameter
and the associated external surface (O.sub.a) of the particle, and
the coefficient of thermal conductivity from the particle into the
surrounding phase and the heat transfer coefficient from the solid
into the gaseous phase, both of which are taken into account by the
coefficient .beta., determine among other things the drawn-off heat
output P.sub.drawn-off according to the following equation:
P.sub.drawn-off=O.sup.a.times..beta..times.(T.sub.catalyst
structure-T.sub.ambient)
[0023] Both P.sub.generated and P.sub.drawn-off can be matched to
one another such that the heat output dissipated from the ignition
area at ambient temperature is less than the heat output generated
in this area, which causes the reaction to start.
[0024] Representative examples of suitable reaction chambers having
reaction and ignition areas include the layers produced by powdered
metallurgy according to EP 0 906 890 A1 (incorporated herein by
reference), in which a powder mixture (reaction area) is added to a
platinum-containing catalyst (ignition area) on an Al.sub.2O.sub.3
substrate during manufacture of discs. The reaction area is formed
of a macroscopic, metal-containing porous substrate structure,
which can also be provided with an additional catalyst insofar as a
catalytically active material (such as copper or dendritic copper)
is not used in the first instance. This substrate structure is
preferably a net-like matrix, which can be obtained by mixing the
catalyst powder with a metal powder and pressing the mixture. In
the pressing process, the metal powder forms a net-like matrix
structure (reaction area), in which the catalyst particles are
"built in" (ignition area). Particularly suited as a starting
material for the metallic matrix are dendritic copper powders,
which can readily be pressed or sintered into a network even with a
relatively low mass proportion of the copper to the total mass of
the layer, have a large surface area and are themselves
catalytically active. When dendritic copper powder is used, for
example, a stabilizing, linking and heat distributing network in
the micron range is obtained.
[0025] In other embodiments, and as illustrated in FIGS. 2a and 2b,
ignition area 2 is formed by a macroscopic, catalyst-containing
porous substrate structure lying adjacent to reaction area 1. This
may be, for example, a catalyst loaded net structure, nonwoven
fabric or foam (ignition area 2) inserted between two heat
exchanger plates 3 coated with catalyst (reaction area 1).
[0026] In general, reaction area 1 and ignition area 2 are present
in the reactor in a spatially mixed configuration or continuously
arranged. Since educts intended for reaction area 1 can react
prematurely in normal operation, ignition area 2 may be located
downstream of reaction area 1. The heating of reaction area 1 then
takes place contrary to the direction of flow, and possibly by way
of solid-state heat conduction from area 2 and, in some cases, by
catalytic self-heating beginning to occur in reaction area 1. Thus,
the reaction front moves forward contrary to the direction of
reactant flow. During normal operation, ignition areas 2 do not
create any problems, since the oxygen for oxidation is consumed
upstream in reaction area 1.
[0027] Such reactors are useful over a wide range of applications,
including (but not limited to) use as a catalytic burner, a
catalytically heated heat exchanger, for partial oxidation,
autothermal reformation, selective CO oxidation or in conjunction
with a fuel cell.
[0028] From the foregoing it will be appreciated that, although
specific embodiments of the invention have been described herein
for purposes of illustration, various modifications may be made
without deviating from the spirit and scope of the invention.
Accordingly, the invention is not limited except as by the appended
claims.
* * * * *