Catalytic converter substrate

Abstract

A catalytic converter substrate comprising a plurality of micro-structured hollow ceramic tubes, each tube having an inside surface and an outside surface, the inside surface having openings to micro-channels distributed radially throughout the tube cross-section, the micro-channels extending from the openings in the inside surface towards the outside surface.

Claims

1. A catalytic converter substrate comprising a plurality of micro-structured tubes, each tube having an inside surface and an outside surface, wherein: at least one of the inside surface and the outside surface has a plurality of openings to micro-channels; and the micro-channels extend from said openings in the at least one surface towards the other surface.

2. The catalytic converter substrate of claim 1, wherein the tubes are ceramic tubes.

3. The catalytic converter substrate of claim 1, wherein the micro-channels extend from openings in the inside surface towards the outside surface.

4. The catalytic converter substrate of claim 1 wherein each tube comprises two distinct layers, the first layer containing the micro-channels extending from the inside surface and terminating within the tube cross-section and a second solid layer at the outside surface.

5. The catalytic converter substrate of any one of claim 4 wherein the second solid layer has a thickness of up to 70% of the thickness of the wall of the micro-structured tubes.

6. The catalytic converter substrate of claim 1, wherein the substrate comprises one or more of: cordierite; zirconia; yttrium stabilised zirconia; titania; silicon carbide; clay; alumina; stainless steel, FeCr alloys; alloys of iron; alloys of aluminium; or sintered metals.

7. The catalytic converter substrate of claim 1, wherein the GSA is in the range 8,000 m.sup.2/m.sup.3 to 15,000 m.sup.2/m.sup.3.

8. The catalytic converter substrate of claim 1 wherein the internal diameter of the micro-structured hollow tubes is from 0.5 to 4 mm.

9. The catalytic converter substrate of claim 1 wherein the wall thickness of the micro-structured hollow tubes is in the range 100 to 500 m.

10. The catalytic converter substrate of claim 1 wherein the micro-channels have an entrance diameter of 5 m to 200 m.

11. The catalytic convertor substrate of claim 1 comprising a catalytically active coating.

12. The catalytic convertor substrate of claim 1 wherein the geometric surface area of the substrate is at least 19,000 m.sup.2/m.sup.3.

13. The catalytic convertor substrate of claim 12, wherein the geometric surface area of the substrate is in the range from 19,000 m.sup.2/m.sup.3 to 35,000 m.sup.2/m.sup.3.

14. The catalytic convertor substrate of claim 1, wherein: the outer diameter of the micro-structured tubes is in the range from 2 mm to 4 mm; and the wall thickness of the micro-structured tubes is in the range from 0.1 mm to 0.8 mm.

15. The catalytic convertor substrate of claim 1, wherein: the outer diameter of the micro-structured tubes is in the range from 2.5 mm to 4 mm; and the wall thickness of the micro-structured tubes is in the range from 0.1 mm to 0.2 mm.

16. The catalytic convertor substrate of claim 1, wherein the outer diameter of the micro-structured tubes is in the range from 2 mm to 4 mm; and the wall thickness of the micro-structured tubes is in the range from 0.2 mm to 1 mm.

17. The catalytic convertor substrate of claim 1, wherein the outer diameter of the micro-structured tubes is in the range from 2.5 mm to 4 mm; and the wall thickness of the micro-structured tubes is in the range from 0.4 mm to 0.8 mm.

18. A catalytic converter comprising a catalytic convertor substrate as set out in claim 1 and having a catalytically active coating, an insulation mat and a substrate housing.

19. The catalytic converter of claim 18 wherein the catalytically active coating is a washcoat.

20. The catalytic converter of claim 18 wherein the coating comprises a precious metal.

21. The catalytic converter of claim 20 wherein the precious metal is a platinum group metal.

22. The catalytic converter of claim 18, wherein the coating comprises a non-precious metal.

23. A kit for a catalytic converter, comprising; a catalytic convertor substrate as a set out in claim 1, an insulation mat; and a substrate housing formed to receive the substrate and mat with a tight fit.

24. An internal combustion engine exhaust system including a catalytic converter as set out in claim 18.

Description

(1) Embodiments of the present invention will now be described by way of example and with reference to the accompanying drawings, in which:

(2) FIG. 1 shows a schematic illustration of the layout and function of a prior art catalytic converter;

(3) FIG. 2 shows a perspective view of the catalytic converter substrate in accordance with the first aspect of the present invention;

(4) FIG. 3 shows a perspective view of a micro-structured hollow ceramic tube of FIG. 2;

(5) FIG. 4 shows a front elevation of a micro-structured hollow ceramic tube of FIG. 2 with an enlarged view of a partial cross section;

(6) FIG. 5a shows a photographic image of the hollow fibres of the ceramic hollow fibre substrate;

(7) FIG. 5b shows a scanning electron micrograph of the cross section of the fibres of the ceramic hollow fibre substrate;

(8) FIG. 5c shows a scanning electron micrograph of the inner surface of the fibres of the ceramic hollow fibre substrate;

(9) FIG. 6 shows a perspective view of the catalytic converter in accordance with the second aspect of the invention with a cut-away section for clarity;

(10) FIG. 7 shows a table comparing embodiments of the invention to conventional catalytic convertor substrates;

(11) FIG. 8 shows a perspective view of the catalytic converter in accordance with the second aspect of the invention;

(12) FIG. 9 shows a schematic representation of the difference between a monolithic prior art substrate and the substrate of the first aspect of the present invention;

(13) FIG. 10 shows a flow diagram of the stages involved in the preparation of an example of an inorganic hollow fibre; and

(14) FIG. 11 shows a table of geometric surface areas and a table of pressure drops for combinations of wall thickness and outer diameter of micro-structured tubes.

(15) A known prior art catalytic converter 1 (see FIG. 1) commonly comprises a ceramic substrate 2 with a precious metal catalytic washcoat 3 layered on top. This is most commonly employed in a three way catalyst system (TWC) which converts hydrocarbons, carbon monoxide and nitrogen oxides to carbon dioxide, water and nitrogen, represented in the following equation:
HC,CO,NO.sub.x.fwdarw.N.sub.2,H.sub.2O,CO.sub.2

(16) The catalytic converter substrate 10 of the present invention (see FIGS. 2 and 5a) comprises a plurality of micro-structured hollow ceramic tubes 20 arranged in a parallel tightly packed bundle. The tubes 20 may be glued together in order to form a rigid substrate. Alternatively, they may be bound together using a strap or, as described below, an insulation mat 70. The tubes 20 are of similar length and each has an internal diameter of approximately 0.8 mm.

(17) Each micro-structured hollow ceramic tube 20 (see FIG. 3) has an inside surface 30 and an outside surface 40, bounding a substantially uniform tube wall 25 which has a thickness of approximately 300 m. The inside surface 30 features a substantially uniform pattern of micro-channel openings 50 (see also FIGS. 4 and 5a) which extend radially into the tube wall 25 as micro channels 55, to a depth of at least 30% of the wall thickness. The micro-channels 55 may be described as being finger-like microvoids. The diameter of the micro-channel openings 50 is from 5 m to 200 m. As the micro-channels 55 terminate inside the tube wall 25, a skin zone 60 of solid tube from the outside surface 40 of the tube 20 may extend up to 70% of the tube wall 25 thickness (see also FIG. 5b). (However, in some embodiments, the channels may extend entirely through the tube wall.)

(18) The catalytic converter 100 according to the second aspect of the present invention (see FIGS. 3 and 8) comprises a substrate 90 comprising a cylindrical, tightly packed, bundle of a plurality of micro-structured hollow ceramic tubes 20 arranged in a parallel formation, having a catalytically active coating (not shown), an insulation mat 70 wrapped around the tubes 20 and a substrate housing 80 surrounding the insulation mat 70. The ends of the tubes 20 are exposed to the atmosphere at either end. In use, the housing 80 forms part of an internal combustion engine exhaust system and is arranged so exhaust gasses pass along the tubes 20. The substrate housing 80 may communicate with an inlet tube. Such an inlet tube may communicate with the exhaust manifold of an internal combustion engine. The substrate housing 80 may communicate with an outlet tube for carrying the exhaust gases to atmosphere.

(19) A comparison of the cross sections of a prior art monolithic catalytic converter 4 and the hollow fibre catalytic substrate tube 20 with a catalytic washcoat 3 (see FIG. 9) shows the difference in geometry. The monolithic substrate 2 has a square cross section outer surface and, after washcoating, a cylindrical inside surface. This results in a non-uniform thickness of catalytic washcoat. The hollow fibre substrate 20, however, has a cylindrical outside surface and a variable inside surface featuring a cylindrical shape, interrupted by a uniform distribution of troughs corresponding to the micro-channels 50 previously described. The catalytic washcoat 3 is deposited on this inside surface 30. The net effect of the differing cross sections is a greater surface area of catalyst in contact with the atmosphere in the inside of the tube 20 for the hollow fibre design as compared to the monolith design, and the use of a smaller quantity of catalytic washcoat 3 to achieve this effect. Also, the micro-channels 50 increase the surface roughness of the tubes which promotes turbulent flow conditions through the tubes, enhancing the effect of the catalyst by increasing contact between exhaust gas and catalyst coating. In the prior art arrangement, the majority of the flow cross-section through the monolith is laminar which reduces the opportunity for exhaust gas-catalyst contact. The increased GSA and increased roughness, promoting mixing act synergistically to improve the performance of the catalyst. This allows a reduction in the amount of catalyst required for a particular performance level. As the catalyst is typically platinum, any reduction in the amount of catalyst required can significantly reduce the cost of any particular catalytic converter.

(20) Some attempts have been made in existing catalytic converters to promote turbulent conditions but those have been done at a macroscopic, mechanical level by including baffles and other such physical formations. Whilst these can generate turbulent eddies in the airflow, turbulent flow is not maintained along the length of the monolith.

(21) The substrate material choice is not restricted to cordierite. Any thermally stable ceramic to which the phase inversion/sintering method can be applied and which will produce a micro-structured hollow ceramic tube will be suitable.

(22) The phase inversion and sintering process described above is known in the prior art. For completeness, there follows a brief example of the steps of the process.

(23) A flow diagram showing the stages involved in the preparation of an inorganic hollow fibre is shown in FIG. 10. The parameters (A to U) for three examples are given below.

(24) A dispersant (D) is dissolved in a solvent (C) prior to the addition of inorganic material (A). This forms a dispersion. In one embodiment, the inorganic material is in the form of a powder with a particle distribution of 1:2:7 (0.01 m:0.05 m:1 m).

(25) The dispersion is rolled/milled. For example, using 20 mm agate balls milling for 48 hours with approximately twice as much alumina/agate by weight as dispersion. A polymer binder (B) is added, after which milling may be continued for up to a further 48 hours.

(26) Preferably, the resulting suspension is transferred to a gas tight reservoir and degassed under vacuum until no bubbles are seen at the surface.

(27) The suspension is then extruded to form a tube (for example, using a 200 ml Harvard stainless steel syringe through a tube-in-orifice spinneret) with an inner diameter (F), and an outer diameter (E). The tube is extruded into a coagulation bath containing a non-solvent (K) for the polymer binder. Optionally, an air-gap (G) of up to 30 cm is provided. If required, a different internal coagulant (I) may be used with a controlled flow rate (J).

(28) The solvent (C) is miscible with at least one of the non-solvent (K) and the internal coagulant (I).

(29) The extrusion rate (H) of the spinning suspension and the flow rate of the internal coagulant is preferably accurately controlled and monitored, for example by two individual Harvard PHD 22/2000 Hpsi syringe pumps to ensure the uniformity of the prepared precursor fibres.

(30) The fibre precursors may be left in the external coagulation bath for an extended period (for example, overnight) to allow for completion of phase inversion of the polymer binder.

(31) Preferably, they are then immersed in an excess of water (e.g. tap water) replaced periodically over a period of 48 hours in order to remove traces of the solvent (C).

(32) Finally, the fibre precursors are calcined in air to yield ceramic hollow fibres with a predetermined sintering profile (L to P).

(33) The sintering process reduces the size of the micro-structured tubes. This results in microtubes having the following properties: Outer diameter (Q); Inner diameter (R); Wall thickness (S); Micro-channel length (T); and Micro-channel width (U).

(34) The table below shows the parameters, A to U, for three examples

(35) TABLE-US-00001 Parameter Example 1 Example 2 Example 3 A Yttrium-stabilized Aluminium oxide Aluminium oxide zirconia (44 wt %) (60 wt %) (60 wt %) B Polyether sulfone Polyether sulfone Polyether sulfone (8 wt %) (6 wt %) (6 wt %) C N-methyl-2- N-methyl- Dimethyl sulfoxide pyrrolidone (33 wt %) pyrrolidone (34 wt %) (34 wt %) D polyethylene glycol (15 Arlacel P135 (0.001 Arlacel P135 (0.001 wt %) g/m.sup.2) g/m.sup.2) E 1.2 mm 1.2 mm 3 mm F 0.8 mm 0.8 mm 1.2 mm G 0 cm 0 cm 0 cm H 7 ml/min 5 ml/min 7 ml/min I N-methyl-2- N-methyl-2- Dimethyl sulfoxide pyrrolidone/water pyrrolidone/water (95 wt %/5 wt %) (95 wt %/5 wt %) J 12 ml/min 3 ml/min 5 ml/min K water water water L Room temperature to Room temperature to Room temperature to 600 C. at 2 C./min 600 C. at 2 C./min 600 C. at 2 C./min M Dwell for 2 hours Dwell for 2 hours Dwell for 2 hours N 600 to 1400 C. at 600 to 1450 C. at 600-1450 C. at 5 C./min 5 C./min 5 C./min O Dwell for 4 hours Dwell for 4 hours Dwell for 4 hours P 1400 C. to room 1450 C. to room 1450 C. to room temperature at temperature at temperature at 5 C./m 5 C./min 5 C./min Q 1.7 mm 1.7 mm 3 mm R 1.1 mm 1.1 mm 1.3 mm S 0.3 mm 0.3 mm 0.85 mm T 0.3 mm (100% 0.28 mm (93% 0.67 mm (78% of fibre wall) of fibre wall) of fibre wall) U 0.02 mm 0.02 mm 0.07 mm

(36) In an exemplary embodiment, the following method was used:

(37) Arlacel P135 at a concentration of 1.3 wt % was dissolved in NMP/water solutions (having 95 wt % N-methyl-2-pyrrolidone and 5 wt % water) prior to the addition of aluminum oxide powders (58.7 wt %) at a ratio of 1:2:7 (for mean particle sizes 0.01 m:0.05 m:1 m) The dispersion was rolled/milled with 20 mm agate milling balls with an approximate alumina/agate weight ratio of 2 for 48 hours. Milling was continued for a further 48 hours after the addition of polyether sulfone (6.1 wt %). The suspension was then transferred to a gas tight reservoir and degassed under vacuum until no bubbles could be seen at the surface.

(38) After degassing, the suspension was transferred to a 200 ml Harvard stainless steel syringe and was extruded through a tube-in-orifice spinneret (with an inner diameter of 1.2 mm, and an outer diameter of 3.0 mm) into a coagulation bath containing 120 liters of water (a non-solvent for the polymer) with an air-gap of between 1-15 cm. Deionised water was used as the internal coagulant and the flow rate ranged from 3 to 21 ml/min. The extrusion rate of the spinning suspension and the flow rate of the internal coagulant were accurately controlled and monitored by two individual Harvard PHD 22/2000 Hpsi syringe pumps, ensuring the uniformity of the prepared precursor fibres.

(39) The fibre precursors were left in the external coagulation bath overnight to allow for completion of phase inversion. They were then immersed in an excess of tap water which was replaced periodically over a period of 48 hours in order to remove traces of NMP. Finally, the fibre precursors were calcined in air (CARBOLITE furnace) to yield ceramic hollow fibre. The temperature was increased from room temperature to 600 C. at a rate of 2 C./min and held for 2 hours, then to the target temperature (1200 C. to 1600 C.) at a rate of 5 C./min and held for 4 hours. The temperature was then reduced to room temperature at a rate of 5 C./min.

EXAMPLES

(40) FIG. 7 shows a table comparing conventional catalytic convertor substrates with embodiments of the invention.

(41) The pressure drop values were calculated based upon a catalytic convertor length of 0.152 m, with a gas viscosity of 1.9e-5 Pa.Math.s, and a volumetric flow rate of 0.025 m3/s. The calculation used the following equation:
deltaP=128*mu*L*Q/pi*d.sup.4
where deltaP=pressure drop, mu=gas viscosity, L=length, Q=volumetric flow rate, and d=channel diameter.

(42) The table shows the number of cells per square cm. OFA is open frontal area (the ratio of the cross-sectional area that is open to the cross-sectional area that is obstructed by the end wall of the micro-structured tubes).

(43) In each example embodiment, the cross-sectional area of the catalytic convertor substrate was 0.0162 m.sup.2, which corresponds to that of the conventional substrates.

(44) This cross-sectional area contains the following numbers of micro-structured tubes: 18,630 tubes of 1 mm outer diameter; 4,633 tubes of 2 mm outer diameter; 2,964 tubes of 2.5 mm diameter; 2,057 tubes of 3 mm diameter; and 1,159 tubes of 4 mm diameter

(45) As can be seen in FIG. 7, standard commercial monolith substrates typically have geometric surface areas in the region of up to about 5,000 m.sup.2/m.sup.3. Embodiments formed in accordance with the invention can achieve geometric surface areas in excess of 19,000 m.sup.2/m.sup.3. The geometric surface area values were measured using mercury intrusion.

(46) Furthermore, not only can greater geometric surface areas be achieved, but also it can be seen that a low pressure drop can be achieved.

(47) Further data is shown in FIG. 11, which includes a table of geometric surface areas and a table of pressure drops for combinations of wall thickness and outer diameter measurements of micro-structured tubes. This data was obtained in the same manner as FIG. 7.

(48) As can be seen in FIG. 11, advantageously low pressure drops can be obtained by embodiments of the invention in which the outer diameter is in the range from 2 mm to 4 mm and the wall thickness is in the range from 0.1 mm to 0.8 mm. Preferably, the outer diameter is in the range from 2.5 mm to 4 mm and the wall thickness is in the range from 0.1 mm to 0.2 mm.

(49) At present, most catalytic convertor substrate have a geometric surface area of up to about 5,000 m.sup.2/m.sup.3 is sufficient for most automotive applications. As can be seen from the table, embodiments of the invention having outer diameters in the range from 2.5 mm to 4 mm and wall thickness in the range from 0.1 mm to 0.2 mm, provide such a geometric surface area, but also achieve an advantageously low pressure drop.

(50) At present, most catalytic convertor substrate lead to pressure drops in the region of 100 Pa to 300 Pa. As can be seen from the table, embodiments of the invention having outer diameters in the range from 2 mm to 4 mm and wall thickness in the range from 0.2 mm to 1 mm, provide such a pressure drop, but also achieve an advantageously high geometric surface area. Preferably, the outer diameter is in the range from 2.5 mm to 4 mm and wall thickness in the range from 0.4 mm to 0.8 mm.

(51) While the invention has been described with a certain degree of particularity, it is manifest that many changes may be made in the details of construction and the arrangement of components without departing from the spirit and scope of this disclosure. It is understood that the invention is not limited to the embodiments set forth herein for purposes of exemplification, but is limited only by the scope of the attached claims, including the full range of equivalency to which each element thereof is entitled.