阅读说明：本技术 用于氧化NO、氧化NH3和选择性催化还原NOx的多功能催化剂 (For oxidation of NO, NH3And a multifunctional catalyst for selective catalytic reduction of NOx ) 是由 K·比尔德 R·多纳 J·M·贝克尔 于 2020-04-30 设计创作，主要内容包括：本发明涉及一种用于氧化NO、氧化氨和选择性催化还原NOx的催化剂,该催化剂包含直通基材,包含钒氧化物以及包含铜和铁中一种或多种的沸石材料中的一种或多种的第一涂层,包含负载于非沸石氧化物材料上的铂族金属组分并且进一步包含钒氧化物和包含铜和铁中一种或多种的沸石材料中的一种或多种的第二涂层以及包含负载于氧化物材料上的铂族金属组分的第三涂层。本发明进一步涉及包含所述催化剂的废气处理系统。(The present invention relates to a catalyst for the oxidation of NO, the oxidation of ammonia and the selective catalytic reduction of NOx comprising a through substrate, a first coating comprising vanadium oxide and one or more of a zeolitic material comprising one or more of copper and iron, a second coating comprising a platinum group metal component supported on a non-zeolitic oxide material and further comprising one or more of vanadium oxide and a zeolitic material comprising one or more of copper and iron, and a third coating comprising a platinum group metal component supported on an oxide material. The invention further relates to an exhaust gas treatment system comprising said catalyst.)

1. A catalyst for the oxidation of NO, the oxidation of ammonia and the selective catalytic reduction of NOx comprising:

(i) a through substrate comprising an inlet end, an outlet end, an axial length of the substrate extending from the inlet end to the outlet end, and a plurality of channels defined by interior walls of the through substrate extending therethrough, wherein interfaces between the channels and the interior walls are defined by interior wall surfaces;

(ii) a first coating comprising one or more of a vanadium oxide and a zeolite material comprising one or more of copper and iron;

(iii) a second coating comprising a platinum group metal component supported on a non-zeolitic oxide material and further comprising one or more of a vanadium oxide and a zeolitic material comprising one or more of copper and iron;

(iv) a third coating comprising a platinum group metal component supported on an oxide material;

wherein the third coating is dispensed on the inner wall surface over z% of the axial length of the substrate from the outlet end to the inlet end, wherein z is in the range of 20 to 80;

wherein the second coating extends over y% of the axial length of the substrate from the inlet end to the outlet end and is dispensed on the inner wall surface, wherein y is in the range of 20-80;

wherein the first coating extends over x% of the axial length of the substrate from the inlet end to the outlet end and is dispensed over the second coating and the third coating, wherein x is in the range of 95-100.

2. The catalyst of claim 1, wherein y is in the range of 20 to (100-z), preferably y is (100-z), wherein z is preferably in the range of 30-70, more preferably 40-60, more preferably 45-55.

3. The catalyst of claim 1 or 2, wherein the first coating comprises a zeolitic material comprising one or more of copper and iron; wherein the zeolitic material contained in the first coating has a framework type selected from the group consisting of AEI, GME, CHA, MFI, BEA, FAU, MOR, mixtures of two or more thereof and mixtures of two or more thereof, preferably from the group consisting of AEI, GME, CHA, BEA, FAU, MOR, mixtures of two or more thereof and mixtures of two or more thereof, more preferably from the group consisting of AEI, CHA, BEA, mixtures of two or more thereof and mixtures of two or more thereof, wherein the zeolitic material contained in the first coating more preferably has a framework type CHA or AEI, more preferably CHA.

4. The catalyst of claim 1 or 2, wherein the first coating comprises vanadium oxide, wherein the vanadium oxide is preferably one or more of vanadium (V) oxide, vanadium (IV) oxide and vanadium (III) oxide.

5. The catalyst of any of claims 1 to 4, wherein 0 to 0.001 wt.%, preferably 0 to 0.0001 wt.%, preferably 0 to 0.00001 wt.% of the first coating is comprised of palladium, preferably palladium, platinum and rhodium.

6. The catalyst of any of claims 1-5, wherein the platinum group metal component contained in the second coating is one or more of platinum, palladium and rhodium, preferably one or more of platinum and palladium, wherein the platinum group metal component is more preferably platinum.

7. The catalyst of any of claims 1-6, wherein the second coating is applied at 0.3 to 10g/ft³Preferably 0.5 to 5g/ft³More preferably 1 to 3g/ft³A loading in a range comprising said platinum group metal component calculated as the elemental platinum group metal;

wherein the second coating preferably comprises the platinum group metal component in an amount in the range of 0.1 to 2 wt.%, more preferably 0.2 to 1 wt.%, more preferably 0.3 to 0.6 wt.%, based on the weight of the non-zeolitic oxide material of the second coating.

8. The catalyst of any one of claims 1-7, wherein the non-zeolitic oxide material on which the platinum group metal component of the second coating is supported comprises, preferably consists of, one or more of alumina, zirconia, titania, silica, ceria, and mixed oxides comprising two or more of Al, Zr, Ti, Si, and Ce, preferably one or more of alumina, zirconia, titania, and silica;

wherein the second coating layer is preferably in the range of 0.1-3g/in³More preferably 0.15 to 1.5g/in³More preferably 0.2 to 0.5g/in³Loadings in the range comprise the non-zeolitic oxide material.

9. The catalyst of any of claims 1-8, wherein the second coating comprises a zeolitic material comprising one or more of copper and iron; wherein the zeolitic material contained in the second coating has a framework type selected from the group consisting of AEI, GME, CHA, MFI, BEA, FAU, MOR, mixtures of two or more thereof and mixtures of two or more thereof, preferably from the group consisting of AEI, GME, CHA, BEA, FAU, MOR, mixtures of two or more thereof and mixtures of two or more thereof, more preferably from the group consisting of AEI, CHA, BEA, mixtures of two or more thereof and mixtures of two or more thereof, wherein the zeolitic material of the second coating more preferably has a framework type CHA or AEI, more preferably CHA.

10. The catalyst of any one of claims 1-9, wherein the second coating and the third coating together have a platinum group metal component loading in the catalyst calculated as elemental platinum group metal in the range of from 1 to 40g/ft³Preferably 2.7 to 25g/ft³More preferably 4.25 to 15g/ft³More preferably 5.5 to 10.5g/ft³Within the range.

11. The catalyst of any one of claims 1 to 10, wherein the platinum group metal component of the third coating is one or more of platinum, palladium and rhodium, preferably one or more of platinum and palladium, more preferably platinum.

12. The catalyst of any one of claims 1 to 11, wherein the oxide material supporting the platinum group metal component contained in the third coating comprises, preferably consists of, one or more of alumina, zirconia, titania, silica, ceria and mixed oxides comprising two or more of Al, Zr, Ti, Si and Ce, preferably one or more of alumina, zirconia, titania and silica, more preferably one or more of titania and silica;

wherein preferably 90 to 100 wt.%, more preferably 95 to 100 wt.%, more preferably 99 to 100 wt.% of the oxide material of the third coating consists of titanium dioxide and optionally silicon dioxide.

13. A method of preparing a catalyst for the oxidation of NO, the oxidation of ammonia and the selective catalytic reduction of NOx, preferably a catalyst according to any of claims 1 to 12, comprising:

(a) providing an uncoated pass-through substrate comprising an inlet end, an outlet end, an axial length of the substrate extending from the inlet end to the outlet end, and a plurality of channels defined by interior walls of the substrate extending therethrough, wherein interfaces between the channels and the interior walls are defined by interior wall surfaces;

(b) providing a slurry comprising a platinum group metal component, an oxide material and a solvent, distributing said slurry over the surface of the inner walls of said substrate over z% of the axial length of the substrate from the outlet end to the inlet end, wherein z is in the range of 20 to 80, calcining the slurry distributed over said substrate to provide a third coating distributed over said substrate;

(c) providing a slurry comprising a platinum group metal component, a non-zeolitic oxide material and one or more of vanadium oxide and a zeolitic material comprising one or more of copper and iron, and a solvent, distributing said slurry on an inner wall surface over y% of the axial length of the substrate from the inlet end to the outlet end, wherein y is in the range of 20 to 80, calcining the slurry distributed on the substrate, resulting in a second coating distributed on the substrate;

(d) providing a slurry comprising vanadium oxide and one or more of a zeolitic material comprising one or more of copper and iron, and a solvent, distributing said slurry on said second coating over x% of the axial length of the substrate from the inlet end to the outlet end, wherein x is in the range of 95 to 100, calcining the slurry distributed on said substrate, obtaining a catalyst for the oxidation of NO, the oxidation of ammonia and the selective catalytic reduction of NOx.

14. A catalyst for the oxidation of NO, ammonia and selective catalytic reduction of NOx, preferably a catalyst for the oxidation of NO, ammonia and selective catalytic reduction of NOx obtainable or obtained by a process according to claim 13.

15. An exhaust gas treatment system for treating an exhaust gas stream from an internal combustion engine, preferably a diesel engine, the exhaust gas treatment system having an upstream end into which the exhaust gas stream is introduced, wherein the exhaust gas treatment system comprises a catalyst according to any of claims 1-12 and 14 and one or more of a selective catalytic reduction catalyst, an ammonia oxidation catalyst and a diesel particulate filter.

Brief Description of Drawings

Figure 1 shows a schematic depiction of a catalyst of the present invention. The figure shows in particular that the catalyst 1 according to the invention comprises a substrate 2, such as a straight-through substrate, on which an inlet coating 3, i.e. a second coating according to the invention, is distributed over 50% of the axial length of the substrate from the inlet end to the outlet end of the substrate and on which an outlet coating 4, i.e. a third coating according to the invention, is distributed over 50% of the axial length of the substrate from the outlet end to the inlet end. The catalyst 1 further comprises a top coat 5 dispensed over the entire length of the substrate on the coating 3 (second coating) and the coating 4 (third coating). Selective catalytic reduction catalyst 14 may generally be present upstream of catalyst 1.

Figure 2 shows the DeNOx performance of the catalysts of comparative examples 1 and 2 and examples 1 and 2 at an inlet temperature of about 200 ℃. and an SV (peak temperature at 160k/h) with ANR of 1.1 and 80 k/h.

FIG. 3 shows the N of the catalysts of comparative examples 1 and 2 and examples 1 and 2 at an inlet temperature of about 200 ℃ and an SV (maximum temperature at 160k/h) of ANR 1.0 and 80k/h₂O is formed.

FIG. 4 shows NO Oxidation (NO) at an inlet temperature of about 200 ℃ and 450 ℃ and an SV of 100k/h for catalysts of comparative examples 1 and 2 and examples 1 and 2₂the/NOX ratio).

Citations

-US 2016/0367973

-US 2016/0367974

Examples

Reference example 1: determination of Dv20, Dv50 and Dv90 values

The particle size distribution was determined by static light scattering using a Sympatec HELOS instrument with the optical concentration of the sample in the range of 5-10%.

Reference example 2: measurement of BET specific surface area

The BET specific surface area is determined using liquid nitrogen in accordance with DIN 66131 or DINISO 9277.

Reference example 3: universal coating method

In order to apply one or more coatings to a through substrate, the through substrate is suitably immersed vertically into a portion of a given slurry at a specific substrate length equal to the target length of coating to be applied. In this way the slurry contacts the substrate walls.

Comparative example 1: preparation of a catalyst not according to the invention (with a Single coating)

Zr-doped alumina powder (20 wt% ZrO)₂BET specific surface area of 200m²In terms of/g, Dv90 was 125 μm and the total pore volume was 0.425ml/g) was added to the solution of platinum amine. The final Pt/Zr-alumina after calcination at 590 ℃ had a Pt content of 1.85 wt% based on the weight of the Zr-alumina. This material was added to water and the resulting slurry was milled as described with reference to example 1 until a Dv90 of 10 microns was obtained. To a Cu-CHA zeolite material (having about 3.75 wt% CuO and SiO)₂:Al₂O₃About 25 molar ratio) to obtain 5 wt% ZrO based on the weight of the zeolitic material after calcination₂. The milled Pt/Zr-alumina slurry was added to the Zr/Cu-CHA slurry and mixed. The final slurry was then distributed over the entire length of an uncoated honeycomb straight-through cordierite monolith substrate (diameter: 26.67cm (10.5 inches) by length: 7.62cm (3 inches) cylindrical substrate having a thickness of 400/(2.54)²Individual cells per square centimeter and 0.1mm (4mil) wall thickness). The substrate is then dried and calcined. The loading of the coating in the catalyst after calcination was about 3.0g/in³Wherein the Cu-CHA loading is 2.6g/in³，ZrO₂The loading capacity is 0.13g/in³Zr-alumina loading of 0.25g/in³Pt loading of 8g/ft³。

Comparative example 2: preparation of a catalyst not according to the invention (with three coats)

Third coat (outlet base coat):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g and Dv90 of 20 microns) so that the Si-titania has a Pt content of 1.1 wt.% based on the weight of the Si-titania after calcination. This material was added to water and the resulting slurry was milled as described with reference to example 1 until a Dv90 of 10 microns was obtained. The resulting slurry (26.67 cm (10.5 inches) diameter by 7.62cm (3 inches) length cylindrical substrate having a 400/(2.54) diameter by 7.62cm (3 inches) length) was then distributed over half the length of the uncoated honeycomb straight-through cordierite monolith substrate using the coating method described in reference example 3 from the outlet side to the inlet side of the substrate²Individual cells per square centimeter and 0.1 millimeter (4mil) wall thickness). The coated substrate is then dried and calcined. After calcination this thirdThe loading of the coating was about 0.51g/in³Including 10g/ft in the third coating³The final platinum loading.

Second coating (full length intermediate coating):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g and Dv90 of 20 microns) so that the Si-titania has a Pt content of 0.35 wt.% after calcination, based on the weight of the Si-titania. This material was added to water and the resulting slurry was milled as described with reference to example 1 until a Dv90 of 10 microns was obtained. To a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃Molar ratio 18) to an aqueous slurry to obtain 5 wt% ZrO based on the weight of the zeolitic material after calcination₂. The Pt-containing slurry was added to the Cu-CHA slurry and stirred to produce the final slurry. The final slurry covering the third washcoat layer was then distributed over the entire length of the honeycomb cordierite monolith substrate that had been coated with the third washcoat layer from the inlet side to the outlet side of the substrate using the coating method described in reference example 3. The coated substrate is then dried and calcined. The loading of the second coating after calcination was 2.5g/in³Including 1.9g/in³ Cu-CHA，0.1g/in³ ZrO₂，0.5g/in³ Si-TiO₂And 3g/ft³The final platinum loading.

First coating (full length topcoat):

to a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃Molar ratio 18) to an aqueous slurry to obtain 5 wt% ZrO based on the weight of the zeolitic material after calcination₂. The final slurry covering the third and second washcoat layers was then distributed over the entire length of the honeycomb through-cordierite monolith substrate coated with the third and second washcoat layers from the inlet side to the outlet side of the substrate using the coating method described in reference example 3. The coated substrate is then dried and calcined. The loading of the first coating after calcination was 1.0g/in³. CalciningThe final catalytic loading (first, second and third coatings) in the catalyst after firing was 3.75g/in³。

Example 1: preparation of the catalyst of the invention (with three coatings)

Third coat (outlet base coat):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g and Dv90 of 20 microns) so that the Si-titania has a Pt content of 0.81 wt.% based on the weight of the Si-titania after calcination. This material was added to water and the resulting slurry was milled as described with reference to example 1 until the resulting Dv90 was 5.2 microns. The colloidal silica binder was finally 2.5 wt% SiO calculated as the weight based on Si-titania after calcination₂The level (from the binder) is mixed into the slurry. The resulting mixture (26.67 cm (10.5 inches) in diameter by 7.62cm (3 inches) length cylindrical substrate having a diameter of 400/(2.54) was then dispensed over half the length of the uncoated honeycomb-like straight-through cordierite monolith substrate from the outlet side to the inlet side of the substrate using the coating method described in reference example 3²Individual cells per square centimeter and 0.1 millimeter (4mil) wall thickness). The coated substrate is then dried and calcined. The loading of the third coating after calcination was about 1g/in³Including 14g/ft in the third coating³Platinum loading.

Second coating (inlet primer):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g, Dv90 was 20 μm) was added to a platinum amine solution. The final Pt/Si-titania after calcination at 590 ℃ had a Pt content of 0.46 wt% based on the weight of the Si-titania. This material was added to water and the resulting slurry was milled as described with reference to example 1 until a Dv90 of 10 microns was obtained. To a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃Molar ratio 18) to an aqueous slurry to obtain 5 weights based on the weight of the zeolitic material after calcinationAmount% ZrO₂. The Pt-containing slurry was added to the Cu-CHA slurry and stirred to produce the final slurry. The final slurry was then distributed over half the length of the honeycomb cordierite monolith substrate coated with the third coating layer using the coating method described in reference example 3 from the inlet side to the outlet side of the substrate to ensure that the second coating layer did not overlap the third coating layer. The coated substrate is then dried and calcined. The loading of the second coating after calcination was about 2g/in³Wherein the Cu-CHA loading is 1.67g/in³，ZrO₂The loading capacity is 0.08g/in³Si-titanium dioxide loading of 0.25g/in³And the PGM loading was 2g/ft³。

First coating (full length topcoat):

to a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃Molar ratio 18) to an aqueous slurry to obtain 5 wt% ZrO based on the weight of the zeolitic material after calcination₂. The slurry covering the third and second washcoat layers was then distributed over the entire length of the honeycomb cordierite monolith substrate coated with the third and second washcoat layers from the inlet side to the outlet side of the substrate using the coating method described in reference example 3. The coated substrate is then dried and calcined. The loading of the first coating after calcination was 1.0g/in³. The final catalytic loading (first, second and third coatings) in the catalyst after calcination was about 2.5g/in³。

Example 2: preparation of the catalyst of the invention (with three coatings)

Third coat (outlet base coat):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g and Dv90 of 20 μm) was added to a platinum amine solution. The final Pt/Si-titania after calcination at 590 ℃ had a Pt content of 0.81 wt% based on the weight of the Si-titania. This material was added to water and the resulting slurry was milled as described with reference to example 1 until the resulting Dv90 was 5.2 microns. Finally, the colloidal silica binder is based on Si-bis after calcinationTitania was mixed into the slurry at a level of 2.5 wt%, calculated on the weight of the titania. The resulting slurry (26.67 cm (10.5 inches) diameter by 7.62cm (3 inches) length cylindrical substrate having a 400/(2.54) diameter by 7.62cm (3 inches) length) was then distributed over half the length of the uncoated honeycomb straight-through cordierite monolith substrate using the coating method described in reference example 5 from the outlet side to the inlet side of the substrate²Individual cells per square centimeter and 0.1 millimeter (4mil) wall thickness). The coated substrate is then dried and calcined. The loading of the third coating in the catalyst after calcination was about 1g/in³Including 14g/ft³Platinum loading.

Second coating (inlet primer):

doping Si with titanium dioxide powder (10% by weight SiO)₂BET specific surface area of 200m²/g and Dv90 of 20 μm) was added to a platinum amine solution. The final Pt/Si-titania after calcination at 590 ℃ had a Pt content of 0.46 wt% based on the weight of the Si-titania. This material was added to water and the resulting slurry was milled as described with reference to example 1 until a Dv90 of 10 microns was obtained. To a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃Molar ratio 18) to an aqueous slurry to obtain 5 wt% ZrO based on the weight of the zeolitic material after calcination₂. The Pt-containing slurry was added to the Cu-CHA slurry and stirred to produce the final mixture. The final mixture was then dispensed from the inlet side to the outlet side of the honeycomb cordierite monolith substrate coated with the third coating layer over half the length of the substrate using the coating method described in reference example 3 to ensure that the second coating layer did not overlap the third coating layer. The coated substrate is then dried and calcined. The loading of the second coating after calcination was about 1g/in³Having a density of 0.71g/in³ Cu-CHA，0.25g/in³Si-Titania with PGM loading of 2g/ft³。

First coating (full length topcoat):

to a Cu-CHA zeolite material (5.1 wt% CuO and SiO)₂:Al₂O₃In a molar ratio of 18)Adding a zirconyl acetate solution to the aqueous slurry to obtain 5 wt% ZrO after calcination based on the weight of the zeolitic material₂. The slurry covering the third and second washcoat layers was then distributed over the entire length of the honeycomb cordierite monolith substrate coated with the third and second washcoat layers from the inlet side to the outlet side of the substrate using the coating method described in reference example 3. The coated substrate is then dried and calcined. The first coating had a loading of 2.0g/in³. The final catalytic loading (first, second and third coatings) in the catalyst after calcination was about 3g/in³。

Example 3: testing of the catalysts of comparative examples 1 and 2 and examples 1 and 2-DeNOx Performance and N₂O formation

These catalysts were evaluated on an engine test unit. The engine in this case is a 6.7L off-road calibration engine. In all cases, each catalyst was tested individually without any upstream oxidation or downstream SCR catalyst. The resulting space velocity was 80k/h for the SCR test (160 k/h for the highest point of temperature). The SCR test was at NH assessed₃And ammonia/NOx ratio (ANR) sweep tests with different stoichiometric ratios between NOx. For the data provided in fig. 2 and 3, NOx conversion is always provided at ANR ═ 1.1 and N is provided₂O formation is always provided at ANR of 1.0 (ANR for ammonia/NOx stoichiometry allows the correct amount of urea to be injected based on a given exhaust mass flow and NOx concentration). 5 SCR inlet temperatures were selected and the engine conditions were appropriately set to achieve the target airspeed. At each engine load (temperature) and ANR step before switching to the next step the catalyst activity is allowed to reach a steady state equilibrium. The NOx conversion provided by fig. 2 and N provided by fig. 3 were measured for the same test₂O is formed.

Figure 2 illustrates that the inventive catalysts of examples 1 and 2 show improved DeNOx over a wide temperature range, i.e., at 200-. Especially at temperatures above 250 c, e.g. 300-500 c, the DeNOx activity of the catalyst comprising a top coat with only the SCR catalyst is greatly improved compared to a catalyst prepared with a single coat of a mixed catalyst. At 450 ℃ (inlet temperature), the inventive catalyst showed about 95% DeNOx, while the catalyst of comparative example 1 (single coating) showed about 50% DeNOx.

FIG. 3 illustrates that the catalyst of the present invention allows for N reduction₂O production, in particular nitrous oxide concentration formed, is less than 15ppm, while in the catalyst of comparative example 1, N is formed₂The O concentration is greater than 20ppm and up to about 60ppm at about 350 ℃. Without wishing to be bound by any theory, it is believed that these results indicate that a top coat comprising only the SCR catalyst may be necessary to control ammonia oxidation at temperatures above 250 ℃.

Example 4: testing of the catalysts of comparative examples 1 and 2 and examples 1 and 2-NO Oxidation

These catalysts were evaluated on an engine test unit. The engine in this case is a 6.7L off-road calibration engine. In all cases, each catalyst was tested individually without any upstream oxidation or downstream SCR catalyst. The resulting space velocity was 100k/h for the NOx oxidation test. Prior to this test, the catalyst was de-greened in situ at 450 ℃ for 2 hours. For the NO oxidation test, the exhaust gas outlet temperature was gradually increased and decreased from 200 ℃ to 500 ℃ to 200 ℃ in 25 ℃ steps while maintaining a constant space velocity. Each step was held for 15 minutes to reach an equilibrium catalyst state. NO Oxidation Activity is reported as NO₂Total NOx ratio (or NO)₂/NOx％)。

Figure 4 illustrates that the catalysts of the invention of examples 1 and 2 show improved NO oxidation compared to the catalysts of comparative examples 1 and 2. This is particularly evident at low temperatures between 200 and 350 ℃ for the kinetic control zone. Furthermore, this low temperature zone is most relevant for passive soot oxidation, as this condition is most representative for daily use. The single coating of comparative example 1 provides slightly greater NO oxidation than examples 1 and 2 at temperatures above 400 ℃ in the diffusion limited regime, but the magnitude of the performance difference is not as significant as in the kinetic control regime.