CA2193115C

CA2193115C - Self-sustaining hydrogen generator

Info

Publication number: CA2193115C
Application number: CA002193115A
Authority: CA
Inventors: Neil Edwards; Jonathon Charles Frost; Ann-Marie Jones; John Frederick Pignon
Original assignee: Johnson Matthey PLC
Current assignee: Johnson Matthey PLC
Priority date: 1994-06-24
Filing date: 1995-06-26
Publication date: 2003-08-19
Anticipated expiration: 2015-06-26
Also published as: EP0766643B1; EP0766643A1; US5762658A; WO1996000186A1; AU683760B2; CA2193115A1; JPH10502047A; ATE174871T1; DK0766643T3; DE69506869D1; ES2126292T3; GB9412786D0; DE69506869T2; AU2749295A

Abstract

A self-starting, self-sustaining hydrogen generator comprises a reactor packed with a mass of mixed catalyst, containing supported copper and palladium. A feedstock, of e.g. methanol and an oxygen source such as air, is injected at high velocity into the mass of catalyst through a multipoint entry such as a tube of porous ceramic. The mass of catalyst is preferably configured concentrically around the tube injector, so that the fluid-flow follows a radial path through the reactor. The product gas is high in hydrogen and can be used as a feed for a fuel cell.

Description

21931~t°5 Self'-sustaining hydrogene generator This invention concerns improvements in reformers, more especially it concerns improvements in self-sustaining reformers that start-up from ambient temperature. The volume-specific hydrogen output of these improved reformers makes them suitable for application in fuel-cell powered vehicles.
We have disclosed in EP 0 217 532, a self-igniting partial oxidation reformer or catalytic hydrogen generator which has become known as the "Hot Spot"
reactor. The basic concept is that methanol and air are co-fed into a reactor containing a packed be;d of copper on refractory support catalyst, with a down-stream zone containing platinum or palladium catalyst mixed with copper catalyst. The down-stream zone provides self-ignition to raise the reactor temperature to a point ' C f f. C P C E f E C
- [ f f C 6 f i f ~ [ ' C
/( f r ' C ~ ' P [ f f t~ [

2 ~ ~~ 31 ~~ l f t t. ' , F f C f f f f f f E C
C C f ~ f t ' ' ~ ' r f.
~ r r o. r o. c r ~ t r a ~xt ~ h, c-(1 a hot spot formed around the point of injection of feedstock into the bed of catalyst.
This concept was further developed in the invention of EP 0 262 947, which uses this reactor design to produce hydrogen from hydrocarbons, but using a catalyst composed of platinum and chromium oxide on a support. Further details have been given in a paper in Platinum Metals Review, 1989, ~, (3) 118-127.
As predicted in the above-mentioned prior art, the use of liquid fuels as hydrogen sources for fuel-cell powered vehicles, or even static systems, is attracting considerable inrE;rest. The best established conversion system is steam reforming, but this is an endothermic ncaction, requiring continuous input of energy. Whilst self-sustaining refornning is clearly an interesting concept, in further studies of the Hot-Spot system, we have found that the reactor as~ described did not permit scale-up, and therefore there was a need to find alternative and improved reactor and/or system designs.
The present invention provides a self-igniting and self-sustaining hydrogen generation reactor for a feedstock fluid comprising an organic fuel in liquid, atomised (spray',, vapour or gas form and a source of oxygen, such as air, said reactor comprising a be;d of a permeable fixed bed of copper-supported catalyst and a PGM-supported catalyst, said reactor further comprising an inlet.for the feedstock which comprises a multiplicity of restricted entries causing high velocity feedstock injection into the bed together with a significant pressure drop and gas expansion, for example an extended swrface area of porous ceramic. Preferably, the inlet is in the form of a AMEP1~3ED SHEET

' c t e. ccee ec eecc. F~
f, s f G f f C (. f. C C f C
l' f E' C G C f. G t C C f C f f C c E < <
-. , ~ f f f R f~ f f f, f f ~ f C
f. P Y. f C f. t l f.~ ~ P f ~ f f ~? 9:>1 1 porous ceramic tube having a closed end, but other inlet designs may give advantages in particular circumstances.
The invention also provides a method for the production of hydrogen from a feedstock comprising passing an organic fuel and a source of oxygen, such as air, over a bed which is a mass of catalyst comprising copper and palladium or other PGM moieties, characterised in that the fuel is in spray, vapour or gas form and further characterised in that the fe;edstock enters the mass of catalyst through a multiplicity of entries which cause a significant pressure drop at least sufficient to prevent back-flow of products and results in high velocity injection of feedstock into the bed and feedstock expansion. For example, the entries may be in the form of an inlet having an extended surf=ace area of porous ceramic.
The porous ceramic used in initial tests was a commercial ceramic of pore size 100~;m, purchased from Fairey, England, and this material is therefore recommended, but we expect that alternative porous ceramic materials will provide _ substantially similar results. It appears that porous metal inlets, whilst having similar gas flow characteristics to porous ceramics, are unsuitable because heat conduction ,.
interferes with the reactions being carried out, and could even cause premature ignition of the methanol/air mixiw-e, for example within the feed tube. However, it is possible that further mat~:rial developments, and/or further reactor design improvements, may permit composirJe metal/ceramic inlet design, which may bring advantages, such as in structural strength.
AMEi~i?ED SHEET ", . WO 96!00186 2 1 ~~ 3 ~ 1 C; 4 The organic fuel c;an be a hydrocarbon or an oxygenate, either in the liquid or gas phase. For ease of description, a liquid oxygenate, methanol, will be referred to in the following description.
In the method of the invention, a hot zone forms around the region where the feedstock enters the rnass of catalyst. It is believed that this hot zone is preferably at a temperature of 350-600°C. In this zone, methanol is partially oxidised to form C02 and H~, and some CO. In a preferred embodiment, water is co-fed with the methanol. The presence of water has several beneficial effects:
(i) It promotes the water-gas shift reaction; thus improving the efficiency of the generator and lowering the concentration of CO in the reformate from 2-8%
to 1-5% by volume, and raising; concurrently the Hz concentration.
(ii) It allows greater thermal control within the catalyst bed.
(iii) Under same conditions, it can react directly with methanol by steam reforming, leading to a high yield of H2.
The water can be pre-mixed with the methanol feed. The water concentration in the aqueous mixture should be between 1% and 40% by mass, with the preferred concentration being in the range 10-30%.
Conventional hydrogen-generators that depend solely or predominantly on the steam-reforming of an organic reactant require continuous input of energy during operation to supply the endothermic heat of reaction. For example, where the organic reactant is methanol:

WO 96/00186 2 ~ 9 3 i 15 5 PCT/GB95/01500 CH30H: + H20 ~~ C02 + 3 H2 eH~B = + 48.96 kJ mol-' In the present invention, self-sustaining hydrogen generation is achieved by catalysing the exothermic conversion of the reactant, so obviating the need for continuous input of energy:
CH30F1 + 1602 -~ C02 + 2 H2 eHz~ _ - 192.86 kJ mof' We have discovered that Cu-based catalysts are very effective for the latter reaction. It is necessary, however, to add a small amount of precious metal catalyst to provide auto-ignition, and to raise the catalyst bed temperature to a level at which the partial oxidation becomes self-sustaining. When the precious metal catalyst is Pd/Si02, containing 3% palladium by mass, it needs only to be present as 5% of the total mass of the catalyst bed in order to induce ignition from room temperature. Other pre-heating methods may be used, however.
It is believed, although we do not wish to be limited to any expression of theory, that there ~~re several key physical and chemical features in the design of an effective self-sustaining p<irtial-oxidation reformer. The flow restriction caused by the porous ceramic creates a pressure drop, resulting in the pore openings acting as small injection points that supply fluid flow at high velocity into the catalyst bed.
Then, in order for the conversion of methanol to occur exclusively by the catalytic partial-oxidation rouge, both the following conditions must apply within the catalyst bed:
(a) the reactant velocity must exceed the homogeneous flame speed, (b) the catalyst must be active enough for the heterogeneous reaction to occur within the short residence time.
To eliminate the possibility of product hydrogen undergoing oxidation, it must be prevented from re-entering a high temperature region in which oxygen is present. To do this, the pressure drop across the ceramic must be high enough to prevent back-flow of products. If the porous ceramic is in the form of a tube or cylinder, the catalyst bed should be arranged concentrically to allow radial flow, and so ensure a minimum path-length through the bed.
It is desirable to reduce or minimise the amount of CO in the product gas fed to the fuel cell. This can be achieved by one or both of passing the product gas over a selective oxidation catalyst that selectively oxidises CO in preference to hydrogen, and passing the product gas over a low temperature water-gas shift catalyst.
The invention will now be illustrated by the following Examples, and with reference to the accompanying drawings which are schematic cross-sections of reactors according to the invention.

A batch of catalyst was made by adding copper(II) ethanoate (71g) to aqueous ammonia, which had been prepared by adding distilled water (3150cm3) to WO 96!00186 .I ~ ~ ~ 7 PCT/GB95/01500 a concentrated solution (0.880) of ammonia (350cm3). This amsnoniacal copper-solution was added to silica spheres (Shell S980B; 750g) in a rotating blender, which was operated for 1 hour to ensure thorough mixing. The silica spheres were then isolated and washed three time, with distilled water, before being dried (110°C;
l6hr) and calcined (4:i0°C; 2t~r). Elemental analysis showed that the resultant copper-loading on the silica spheres was 1.9% (by mass). Before being loaded into hydrogen-generator, the: catalyst was activated by reduction (400°C;
2hr; 10%H?/N~.
A schematic diagram of the hydrogen-generator is shown in Figure 1.
The reactor shell consisted of ai stainless cylinder (height l7cm, diameter 9cm), 1, having a main inlet aperture, 2, and an outlet aperture, 3, to which was attached an outlet tube, 4. Fitted through die aperture 2 was a feedstock inlet tube, 5, having a flange, 6. Fitted and sealed to a stainless flange 6 was a porous ceramic tube, 7, held under compression by and sealed to a stainless steel clamping bar, 8. The feedstock inlet tube 5? had an L-shaped manifold, 9, into which was fed an air line, 10, and a feed line for t:he liquid feed, 11. The liquid-feed line 11 was coiled around the inlet tube 5 for heat exchange, before terminating mid-way down the porous ceramic tube 7. In this embodiment, a further air line, 12, entered the reactor 1 and . was coiled around the reactor wall, for preheating the air, before entering the manifold 9. In this configuration, the fluid emerged radially from the porous ceramic tube, but it then followed an axial path through most of the catalyst bed.
The volume of the catalyst bed was 850cm3.

WO 96100186 219 31 15 g pCT/GB95/01500 A mixture comprising 85% methanol (by mass) in water was injected (at a rate of 5.2cm3 miri') into the catalyst bed through the porous ceramic tube (dimensions: 3cm diameter, 4cm long; pore diameter: 100pm). The exit stream was cooled to remove any condensable components, and the dry gas was analysed for H2, CO, C02, OZ and Nz.
The bed temperature was raised (by applying an external heat source) until the onset of reaction, which occurred at ca 150°C; the external heating was then switched off. The composition of the exit stream was recorded as a function of time-elapsed after the onset of reaction (Table 1).
A steady state was reached after about 20 minutes of operation, when the hydrogen yield levelled at 245 litres h-1. When the volume of catalyst was taken into account, the specific output of hydrogen at steady-state was 290 litres per hour per litre of catalyst. At this stage, the maximum temperature within the catalyst bed (in the immediate vicinity of the ceramic tube) stabilised at ca 600°C, whereas the temperature inside the tube remained <100°C. Furthermore, the efficiency of the generator was close to 100% (ie each molecule of methanol converted produced 2 molecules of hydrogen). When the water was excluded from the reactant-feed, the efficiency declined to 92%.

WO 96/00186 ?CT/GB95/01500 Output of axial hydrogen-generator with 4cm long ceramic injector and 850cm3 catalyst bed; composition of reformate and hydrogen-yield Time elapsed 2 min 15 min 25 min 30 min H2 / % 30 31 39 39 CO/% 3 2 2 1.8 COZ / % >20 >20 18 19 O~/% 0 0 0 0 N2 / % 37 37 39 39 H2 yield 1180 195 245 246 /
litres h'' The procedure described in Example 1 was followed, except that a longer ceramic injector (dime,nsions: 3cm diameter, 6cm long) was used and the reactant feed-rates were increased (85% methanol/water 7.6cm3 min-1; air 9000cm3 mini'). After onset of reaction, the generator reached a steady-state after about 15 minutes of operation (Table 2). In this case, the specific hydrogen output at steady state was 420 litres per hour per litre of catalyst.

Output of axial hydrogen-generator with 6cm long ceramic injector and 850cm3 catalyst bed; composition of reformate and hydrogen-yield.
5 Time elapsed 10 min 15 min 25 min 30 min 40 min HZ / % 32 35 36 36 36 CO / % 4 4 4 4.5 5 COZ / % 16 16 16 16 16 10 OZ/% 0 0 0 0 0 N2 / % 36 36 37 37 37 HZ yield 307 358 355 351 362 /
litres h-' The hydrogen-generator shown in Figure 1 was modified, as shown in Figure 2, to allow radial flow through a smaller bed (120cm3) of catalyst.
As Figure 2 shows, the catalyst bed, 21, was the same length (6cm) as the porous ceramic tube, 22. The bed was enclosed by a copper gauze, 23, which allowed the products to emerge radially. Axial flow through the bed was prevented by the presence of two impervious ceramic plugs, 24 and 25.
The catalyst was prepared and activated in the way described in Example 1. Neat methanol was injected (at a rate of 3.6cm3 miri') together with air (2500cm3 miri') into the catalyst bed through the porous ceramic tube. An external WO 96/00186 ? ~ PCTlGB95/01500 '_ ~ ~ 11 heat source was applied., but only until the onset of reaction. After onset, a steady state was quickly reach's (within 3 minutes), where the specific hydrogen output was 690 litres per hour per litre o~f catalyst (Table 3). By increasing the air feed-rate (to 4000cm3 miri '), the hydrogen yield was increased to a maximum of 93 litres h'', which corresponded to a specific; output of 775 litres per hour per litre of reactor.

Output of radial hydrogen-generator with 6cm long ceramic injector and 120cm' catalyst heel; composition of reformate and hydrogen-yield.
Time elapsed 3 min 25 min 45 min 60 min HZ / % 32.5 32 33 32 CO/% 5 5.5 4 3.5 COZ/% 16 15.5 16.5 16.5 OZ/% O O O O

NZ / % 43 43 42 42 H2 yield 86 80 84 81 /
litres h'' A 5%Cu/AIzO~ catalyst (nominal composition by mass) was prepared by adding copper(II) ethanoate (82.4g) to a concentrated solution (0.880) of ammonia (320cm3). The resultant solution was added slowly to alumina extrudate (Norton WO 96/00186 2 ~ 9 31 1 J 12 pCT~GB95/01500 6173; SOOg) in a rotating blender. The extrudate was then heated under nitrogen, using a water bath, until the individual pellets had changed colour (from deep blue to pale blue), indicating that most of the ammonia had been removed. The pellets were subsequently dried ( 110°C; l6hr), calcined (400°C; 2hr), and activated (400°C;
2hr; 10%Hz/NZ).
The same preparative steps were also used to make a smaller batch of 5%Pd/A1203 catalyst, starting from palladium(II) ethanoate (2.64g) and alumina extrudate (same source as above; 23.75g).
The 5%Cu/A1203 and S%Pd/A1~03 catalysts were mixed together in a ratio of 19:1 by mass. The resulting catalyst mixture was packed as a thin radial bed (2.Smm deep), which fitted concentrically around a porous ceramic tube ( 1 l.4cm long; 3cm diameter) and was held in place by a copper gauze ( 1 l.4cm long;
3.Scm diameter). The volume of catalyst mixture used in the radial bed was only SScm3.
An atomised liquid feed comprising 85% methanol (by mass) in water was injected (at a rate of 3.1cm3 miri') together with air (3000cm3 miri') through the porous ceramic tube into the cold (20°C) bed of mixed catalyst. The bed temperature began to rise immediately, and within a minute it was approaching the steady-state maximum (500°C). At steady-state, the average hydrogen yield was 175 litres h-' (Table 4), which corresponded to a specific hydrogen output of litres per hour per litre of catalyst. The radial catalyst bed and the porous ceramic tube contained within it, could be enclosed in a 150cm3 canister. When the volume WO 96/00186 V~ , ~ ~ 13 . PCT/GB95/01500 of the canister was take;n into account, the reactor-specific hydrogen output was 1150 litres per hour per litre; of reactor.

Steady-state output of radial hydrogen-generator with 11.4cm long ceramic injector and -'i5cm3 catalyst bed, operating at 100% methanol conversion;
composition of reform~ate and hydrogen yield.
Time elapsed 165 nun 190 min 215 260 min 290 min 315 min min H2 / % 41.7 43.5 41.7 40.4 40.6 40.4 CO / % 2.9 3.1 3.1 3.1 3.2 3.3 C02 / % 19.:i '19.7 19.7 18.3 18.1 18.3 02/% 0 0 0 0 0 0 NZ / % 35.:3 :31.6 33.9 36 35.1 35.6 ~, H2 yield 174 182 187 165 170 164 /
litres h-' ~ When she react;3nt stoichiometry was changed to a methanol-rich feed (85% methanol/water; 3.Scm3 miri '; air: 2500cm3 mini '), the average hydrogen yield at steady-state rose to 200 litres h-' (Table 5). At the same time, the bed temperature decreased to 370°C, and the methanol conversion dropped from 100% to 70%.
However, the hydrogen concentration in the product stream was higher than expected WO 96/00186 ~ ~ C~ 3 ~ ~ C~ PCT/GB95/01500 (on the basis of all the converted methanol undergoing partial oxidation), indicating that some of the hydrogen was being generated by steam reforming.
Under the methanol-rich conditions, the specific hydrogen output was 3600 litres per hour per litre of catalyst, or 1300 litres per hour per litre of reactor when the volume of the canister was taken into account.

Steady-state output of radial hydrogen-generator with 11.4 long ceramic injector and SScm3 catalyst bed, operating at 70% methanol conversion;
composition of reformate and hydrogen yield.
Time elapsed 65 min 225 315 min 410 min 560 min 1050 min min HZ / % 48.1 47.0 45.9 46.9 47.0 46.8 CO / % 2.3 2.4 2.8 2.7 2.6 2.8 COZ / % 19.6 18.3 19.2 19.5 19.2 18.2 OZ/%O O O O O O O

NZ / % 27 28 29.7 28 27.2 27.3 HZ yield 192 175 206 219 200 198 /
litres h~1 WO 96/00186 ~ ,.) PCT/GB95/01500 The copper/silica catalyst, as prepared and activated in Example 1, was tested in a reactor fitted with a single point-injector (as described by 5 J W Jenkins, EP 0 21'7 532. Using the same proportions of methanol/water/air as in Examples l and 2, hydrogen-yields which were below 10 litres h'' could be generated. However, in order to achieve higher yields (up to a maximum of 15 litres h''), a continuous source of external heating (250W) had to be applied.

Claims

1. A self-sustaining hydrogen generator reactor for a feedstock comprising an organic fuel in liquid spray, vapour or gas form and a source of oxygen, said reactor comprising a permeable mass of catalyst, and said reactor further comprising an inlet for the feedstock which comprises a porous member provided with pore openings that act as injection points, through which the feedstock is injected at high velocity into the bed, and providing feedstock fluid expansion and a substantial pressure drop at least sufficient to prevent flow-back of feedstock or products.

2. A reactor according claim 1, wherein the inlet comprises an extended area of porous ceramic with a majority of the external surface area in contact with a bed of catalyst.

3. A reactor according to claim 2, wherein the porous ceramic is in the form of a tube, with a radial catalyst bed held concentrically around it.

4. A reactor according to any one of claims 1 to 3, wherein the catalyst contains supported copper.

5. A reactor according to any one of claims 1 to 4, including means to provide pre-heating.

6. A reactor according to any one of claims 1 to 4 which includes a caralyst that allows start-up from ambient temperature.

7. A method for the self-starting, self-sustaining production of hydrogen from a feedstock comprising passing a fuel and a source of oxygen over a mass of catalyst comprising copper and precious metal moieties, characterised in that the feedstock enters the mass of catalyst through a porous member causing a significant pressure drop with high velocity injection of feedstock into the mass of catalyst, ana flow-back of feedstock or products is prevented.

8. A method according to claim 7, wherein a hot zone exists in the catalys mass close to the injection point.

9. A method according to claim 8, wherein the hot zone is at a temperature of approximately 150-600°C.

10. A method according to any one of claims 7 to 9, wherein water is simultaneously injected into the catalyst mass with the feedstock.

11. A method according to claim 10, wherein the added water reacts with some of the methanol to generate hydrogen.

12. A method according to any one of claims 7 to 11, wherein the CO
concentration of the product gas is reduced by passing said product gas over a low temperature water-gas shift catalyst.

13. A method according to any one of claims 7 to 11, wherein the CO
concentration of the product gas is reduced by passing said product gas together with an added source of oxygen over a catalyst that selectively oxidises CO in preference to hydrogen.

14. A method according to any one of claims 7 to 11, wherein the CO
concentration of the product gas is reduced by passing said product gas over a low temperature water-gas shift catalyst and then a selective oxidation catalyst in succession.

15. A method according to any one of claims 7 to 14, wherein the fuel is methanol.

16. A fuel cell system comprising a hydrogen generator reactor according to any one of claims 1 to 6.