CA1081916A - Monolithic-supported catalyst or groups of monolithic- supported catalysts for the purification of waste gases of internal combustion engines - Google Patents
Monolithic-supported catalyst or groups of monolithic- supported catalysts for the purification of waste gases of internal combustion enginesInfo
- Publication number
- CA1081916A CA1081916A CA261,936A CA261936A CA1081916A CA 1081916 A CA1081916 A CA 1081916A CA 261936 A CA261936 A CA 261936A CA 1081916 A CA1081916 A CA 1081916A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- waste gases
- catalysts
- monolithic
- flow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 239000002912 waste gas Substances 0.000 title claims abstract description 42
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 8
- 238000000746 purification Methods 0.000 title claims abstract description 8
- 239000012072 active phase Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002574 poison Substances 0.000 claims description 4
- 231100000614 poison Toxicity 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 238000009827 uniform distribution Methods 0.000 claims description 3
- 230000002779 inactivation Effects 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052697 platinum Inorganic materials 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 206010063493 Premature ageing Diseases 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 239000013543 active substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000010953 base metal Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- -1 as for example Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/19—
-
- B01J35/56—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
- F01N13/0097—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are arranged in a single housing
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a monolithic-supported catalyst or group of monolithic-supported catalysts for the purification of waste gases of internal combustion engines.
Such catalyst or group of catalysts has an increasing content of active phases, e.g. platinum in the direction of flow of the waste gases. Such a catalyst is not subject to premature ageing or poisoning in use in the purification of the waste gases.
The present invention provides a monolithic-supported catalyst or group of monolithic-supported catalysts for the purification of waste gases of internal combustion engines.
Such catalyst or group of catalysts has an increasing content of active phases, e.g. platinum in the direction of flow of the waste gases. Such a catalyst is not subject to premature ageing or poisoning in use in the purification of the waste gases.
Description
The present invention relates to a monolithic supported catalyst, groups of such catalysts and groups of conventional monolithic catalysts which avoid premature ageing of -the catalyst by damage to the active phase, particularly by catalyst poisons, in the cataly-tic purification of the waste gases o~ internal combustion engines.
Because of the constantly increasing number of motor vehicles pollution of the air has become a serious problem for the solution of which the catalytic processes are of the greatest importance among the processes proposed and those already applied. With respect to activity, extended time activity and mechanical stability the catalysts used must satisfy the highest requirements. Apart from low-porosity catalysts, monolithic-supported catalysts are primarily used.
The latter catalysts can be produced from cordierite, mullite, aluminium oxide, silicon carbide or metallic alloys. Because of their honeycomb structure and the ducts extending parallel to the direction of flow of the waste gases they do not cause any significa~t pressure loss but they can influence the duct cross section and shape as well as the mass transport and thus the catalytic activity of the system.
The ac*ive phases, such as noble metals, oxidic compounds of base metals or combinations of the two metals usually are appliedo~the monolithic catalysts as thin films. For better distribution of active phases on the support bodies low-surface skeleton bodies are provided with a very thin high-surface intermediate support film. The oxides of copper, chromium, manganese, iron, cobalt, nickel and combinations thereof, as for example, copper chromite, are suitable as base metals.
From the groups of noble metals platinum, palladium, rhodium and rhuthenium are used. Further modifications are obtained by doping the base metals with noble metals or noble metals with base metals or their compounds. In many cases small amounts of other elements are added to said substances as promoters for improving specific properties of the catalyst system, for example, from alkaline earth metals such as magnesium, calcium, s-trontium and barium, from the rare earth metals, as for example, samarium, lanthanium and cerium, or from the fourth groupof the periodic system such as -titanium and tin.
These active phases can change during operation due to ageing or poisoning of the catalyst.
Primarily the fuel additives and the motor-oil additives and their decomposition products, in addition to the relatively high operating temperatures, affect the activity of the catalysts.
These additives include lead alkyls (antiknock agents), alkyl halides, phosphorus, sulphur and zinc compounds. Lead compounds, which are contained in the waste gases in the form of aerosols, damage noble-metal-containing catalysts to provide catalyst poisoning.
The present invention provides a monolithic-supported catalyst or groups of monolithic-supported catalysts for the purification of the waste gases of internal combusion engines, i.e., a catalyst which is not subject to premature ageing or poisoning.
In accordance with the present invention there is provided a monolithic-supported catalyst or groups of monolithic-supported catalysts for the ~urification of the waste gases 6Z c~Jn~
of internal combustion engines which has ~ increasing content of active phases in the direction of flow of the waste gases.
The catalyst according to the present invention thus is characterized in that its content of active phases in the direc-tion of flow of the waste gases has a positive gradient.
The increase in the concentration of active phases (i.e., the concentration of active substances) per unit of length ~.~8~
of the monoli-thic-supported catalyst is regarded as a positive gradient for the content of active phases. Depending on both -the intended use and the method of production the value of the gradient can vary fundamentally within a monolithic-supported ca-talyst. Thus, for example, at the inlet end of the catalyst the gradient can be very small and can increase towards the outlet end. However, it can also be very large at the inlet end and decrease towards the outlet end. It can be of the order of 6xlO 5 to 3xlO 1 % per millimetre, preferably from 6xlO 4 to 3xlO 2 % per millimetre.
According to a preferred very variable modification of the invention at least two of these catalysts having different gradients for the content of active phases in the direction of flow of the waste gases are arranged in series as one group.
Thus, according to the invention in a group comprising three monolithic catalysts the first catalyst has a low positive gradient for the content of active phases, the second catalyst has a medium positive gradient and the third catalyst a high positive gradient. Groups of two single catalysts are preferred, !~
but in special cases up to four and more catalyst units can be connected in series.
The individual catalysts can be coated with active phases or active substances having identical or different compositions. This permits the optimum utilization of the ; ~
different effects of the individual catalysts, for example, ~ -with respect to both the starting temperature and the rate of reaction of deleterious substances.
Another modification, which is effective in the same direction, relates to a group of conventional monolithic-supported catalysts each of which has a uniform distributionof the content of active phases or active substances. At least two of these catalysts are connected in series in the direction of flow of the waste gases so that the rearward catalyst always has a content of active phases which is higher than that of the preceding catalyst. This arrangement also satisfies the condition of the invention, namely to provide an increasing content of active phases in the direction of flow of the waste gases and thus use a positive gradient for the content of active phases along the entire group. For example, a group comprising three monolithic catalysts thus provides a low concentration of active substances at the first catalyst a medium concentration at the second catalyst and a high concentration at the catalyst in the end position. However, within a discrete catalyst the active substance is uniformly distributed over the catalyst length.
In a modification of the invention the individual catalysts can also be coated with active phases having identical or different compositions of substances in order to obtain an optimum effect of the entire group.
When using a group of catalysts, two to four or more catalysts being feasible it depends on the individual case whether catalysts having different gradients for the content of active phases or two to four or more catalyst units having uniform coating with active substance are combined or whether according to a further modification of the invention the two types of catalyst, i.e., that according to the invention and a conventional catalyst, are combined.
The supported catalyst according to the invention or the catalyst groups according to the invention have the advan-tage that smaller amounts of active phases are rendered catalytically inactive due to loading with toxic agents because endurance tests on vehicles have shown that the catalyst poisons from fuel and oil are primarily deposited in the region of the waste gas inlet of the monolithic-supported catalysts, where ' they result in a substan-tially more intense deactivation than in ~he regions fur-ther downstream.
For the catalytic purification more active phase is available over a longer operating time since -the deactivation in the rear region of -the catalyst or of the yroups of catalysts is much slower and its extent is much smaller. The service life of the catalyst according to the invention is substantially longer than that of the known catalysts.
Moreover, according to the invention an increasing concentration of active phase in a direction towards the waste gas outlet of the catalyst or of the groups of catalysts has the advantage that as the concentration of combustible substances in the waste gas decreases and as the reaction thus becomes more difficult an increasing concentration of active substances is available which to some extent compensates for a decrease in the conversion and thus improves the overall efficiency of the catalyst.
The present invention will be further illustrated by way of the accompanying drawings in which, Figure 1 is a schematic of a monolithic-supported catalyst, according to one embodiment of the presen-t invention, disposed in a catalyst housing, Figure 2 is a graphic representation of feasible distri-bution curves for the content of active phases of the catalyst according to Figure 1 with a positive gradient, Figure 3 is a schematic of a group of three monolithic-supported catalysts according to another embodiment of the present invention, Figure 4 is a graphic representation of feasible distri-bution curves for the content of active phase of the catalysts of the group according to Figure 3 with positive gradlents, Figure 5 is a diagrammatic representation of a group ' according to a further embodiment of the present invention in which monolithic-supported catalysts are connected in series, each catalyst having a uniform distribution of the content of active phases in the direc~ion offlow of the waste gases.
Figure 6 is a diagrammatic representation of -the con-tents of active phase of -the individual monolithic catalysts according to Figure 5.
According to Figure 5 the ca-talyst portion 2 has a higher content of uniformly distributed active phase than that of the catalyst portion 1. The catalyst portion 3 has a higher content of uniformly distributed active phase than that of the catalyst portion 2.
The present invention will be further illustrated by way of the following Examples.
Example 1 A monolithic-supported catalyst produced by means of the dip-tank method and having a length of 150 mm is divided into 10 segments of 15 mm length in order to determine the content of active phase. The segments have the following content of platinum in % by weight:
segment 1 0.5 segment 2 0.28 segment 3 0.22 segment ~ 0.21 segment 5 0.20 segment 6 0.20 segment 7 0.21 segment 8 0.26 segment 9 0.28 segment 10 0.74 In a conversion test of this catalys-t in the fresh state the following results are obtained:
CO max. 98.04%
HC max. 77.33%
The results of the degree of conversion in % are obtained from the following equation:
100 x inlet concentration-outlet concentration inlet concentration E ample 2 The monolithic-supporte~ catalyst according to Example 1 is divided between the segments 5 and 6. ; ?
The two halves are so arranged in series in a device that the intersecting planes are pointing agalnst the direction of flow of the waste gases.
The conversion test of the fresh catalyst provided the following values: CO max. 98.0%, HC max. 78.71%.
The gradients (differences in content of Pt between the segments) in the direction of flow of the waste gases are:
+0.01% by weight/15 mm and +0.01% by weight/15 mm +0.01% by weight/15 mm +0.05% by weight/15 rmn +0.06% by weight/15 mrn +0.02% by weight/15 mm +0.22% by weight/15 mm +0.46% by weight/15 mm Over their entire length the two catalyst portions have a gradient of active phase of -~ 0.30%/75 mm and + 0.54%/75 mm.
_xample 3 A catalyst obtained according to Example 2 is aged for -~
100 hours at a waste gas temperature of 720C at the engine and is subsequently subjected to a conversion test. For CO max. and HC max. 98.04% and 74.74%, respectively, are obtained as degree of conversion. , The starting behaviour, which results from the ternperature ~ ;
at which predetermined amounts of conversion are attained, serves as a further measuring value for the quality of a catalyst for the purificakion of the waste gases from internal combustion engines. The higher the value obtained for the temperature the poorer will be the starting behaviour of the catalyst.
For the aged catalyst the following measured values for the starting behaviour were obtained:
50% CO - ~ 324C
90~ CO ~ 339C
50% HC ~ 336C
70% HC ~ 391C
Example 4 A monolithic-supported catalyst according to Example 1 is aged for 100 hours at a waste gas temperature of 720C
at the engine and then subjected to a conversion test. The values for CO max. and HC max. are 98.0~ and 71.35% respectively.
The starting behaviour is determined in the manner descrbied in Example 3.
The following measured data are obtained for the aged catalyst:
50% CO - ~ 325C
90% CO ~ 360C
50% HC - -~ 350C
70% HC ~ 437C
Thus, it is immediately evident from the Examples 3 and 4 that the catalyst according to the invention and the device according to the invention show improved ageing and starting behaviour.
Example 5 A monolithic-supported cordierite catalyst coated with active phase by means of the dip tank method according to the laid-open German Specification 2,306,395 and having a length of 150 mm is divided into 7 segments (each segment having a length of 21.4 mm) in order to determine the content of active phase. These segments have the following platinum contents in % by weight:
segment 1 0.185 segment 2 0.172 segment 3 0.170 segment 4 0.168 segment 5 0.172 segment 6 0.174 segment 7 0.21 ~ For the entire catalyst monolith, a platinum content of 1.65 g ~ 11 mg per mm is obtained. As is evident from the above values said platinum content is distributed over the ;
entire catalyst monolith in almost constant concentration. In the conversion test in the fresh state of the catalyst monolith the following values are obtained:
CO max. 99 %
HC max. 80.5%
Its starting behaviour is characteristic of this catalyst and is obtained from the temperatures at which 50 and ~, 90% CO as welI as 50 and 70% of HC are converted.
For the monolithic-supported catalyst according to - -example 5 the following values are obtained for the starting behaviour:
50% CO ~ 249C ~ .
90% CO ~ 283C
50% HC ~ 263C
70% HC - ~ 285C ~
Example 6 ~ -Two monolithic-supported catalysts coated differently with active phase by means of the dip tank method according to the laid-open German Specification 23 06 395 (each catalyst having a length o~ 75 mm) are divided into 4 segments (each segment having a length of 18.75 mm) in order to determine the ;~ ' conten-t of active phase. The following platinum contents are determined:
monolith 1 monolith 2 segment 1 0.197% by weiyht segment 1 0.252% by weight segment 2 0.193% by weight segment 2 0.252% by weight segment 3 0.194% by weight segment 3 0.249% by weight segment 4 0.210% by weight segment 4 0.253% by weight ~.
For the entire catalyst monoliths platinum contents .
of 0.6 g or 8.28 mg per mm of catalyst length and 0.9 g or 12.41 mg per mm of catalyst length are obtained.
The catalyst monoltihs 1 and 2 are so secured to a waste-gas purifying device that the catalyst monolith 1 is arranged in the direction of the flow of waste gases in front of the catalyst monolith 2.
In the conversion test in the fresh state the following values are obtained for the catalyst monoliths arranged in series:
CO max. 98%
HC max. 80%
For the starting behaviour the following temperatures are determined:
50gO CO - ~ 239C
90% CO 1 280C
50% HC - "~ 261C
70%O HC~ ~ 283C
_xample 7 ..
The monolith-supported catalyst according to Example 5 is aged for 100 hours at the engine and then subjected to a conversion test. The following values are obtained:
CO max. 98 %
HC max. 74.3%
For the starting behaviour the following temperatures are determined:
50% CO - -~ 343C
90% CO ---t 386C
50%~HC - ~ 360C
90% HC - -~ 404C
Example 8 The catalyst monoliths 1 and 2 arranged according to example 6 are aged for 100 hours at a waste gas temperature of 720C at the engine.
In the conversion test the following values are obtained.
CO max. 98 %
HC max. 77.5%
For the starting behaviour the following temperatures are determined:
50% CO ~ 332C
90~ CO ~ 355C
50% HC ~ 335C ~ ;
70% HC ~ 365C
It is clearly evident from the examples that in the device according to the invention the catalyst monoliths have a better conversion and starting behaviour and thus a better endurance test activi-ty after the ageing, despite the lower content of active phase. ~ ;
".~
.
Because of the constantly increasing number of motor vehicles pollution of the air has become a serious problem for the solution of which the catalytic processes are of the greatest importance among the processes proposed and those already applied. With respect to activity, extended time activity and mechanical stability the catalysts used must satisfy the highest requirements. Apart from low-porosity catalysts, monolithic-supported catalysts are primarily used.
The latter catalysts can be produced from cordierite, mullite, aluminium oxide, silicon carbide or metallic alloys. Because of their honeycomb structure and the ducts extending parallel to the direction of flow of the waste gases they do not cause any significa~t pressure loss but they can influence the duct cross section and shape as well as the mass transport and thus the catalytic activity of the system.
The ac*ive phases, such as noble metals, oxidic compounds of base metals or combinations of the two metals usually are appliedo~the monolithic catalysts as thin films. For better distribution of active phases on the support bodies low-surface skeleton bodies are provided with a very thin high-surface intermediate support film. The oxides of copper, chromium, manganese, iron, cobalt, nickel and combinations thereof, as for example, copper chromite, are suitable as base metals.
From the groups of noble metals platinum, palladium, rhodium and rhuthenium are used. Further modifications are obtained by doping the base metals with noble metals or noble metals with base metals or their compounds. In many cases small amounts of other elements are added to said substances as promoters for improving specific properties of the catalyst system, for example, from alkaline earth metals such as magnesium, calcium, s-trontium and barium, from the rare earth metals, as for example, samarium, lanthanium and cerium, or from the fourth groupof the periodic system such as -titanium and tin.
These active phases can change during operation due to ageing or poisoning of the catalyst.
Primarily the fuel additives and the motor-oil additives and their decomposition products, in addition to the relatively high operating temperatures, affect the activity of the catalysts.
These additives include lead alkyls (antiknock agents), alkyl halides, phosphorus, sulphur and zinc compounds. Lead compounds, which are contained in the waste gases in the form of aerosols, damage noble-metal-containing catalysts to provide catalyst poisoning.
The present invention provides a monolithic-supported catalyst or groups of monolithic-supported catalysts for the purification of the waste gases of internal combusion engines, i.e., a catalyst which is not subject to premature ageing or poisoning.
In accordance with the present invention there is provided a monolithic-supported catalyst or groups of monolithic-supported catalysts for the ~urification of the waste gases 6Z c~Jn~
of internal combustion engines which has ~ increasing content of active phases in the direction of flow of the waste gases.
The catalyst according to the present invention thus is characterized in that its content of active phases in the direc-tion of flow of the waste gases has a positive gradient.
The increase in the concentration of active phases (i.e., the concentration of active substances) per unit of length ~.~8~
of the monoli-thic-supported catalyst is regarded as a positive gradient for the content of active phases. Depending on both -the intended use and the method of production the value of the gradient can vary fundamentally within a monolithic-supported ca-talyst. Thus, for example, at the inlet end of the catalyst the gradient can be very small and can increase towards the outlet end. However, it can also be very large at the inlet end and decrease towards the outlet end. It can be of the order of 6xlO 5 to 3xlO 1 % per millimetre, preferably from 6xlO 4 to 3xlO 2 % per millimetre.
According to a preferred very variable modification of the invention at least two of these catalysts having different gradients for the content of active phases in the direction of flow of the waste gases are arranged in series as one group.
Thus, according to the invention in a group comprising three monolithic catalysts the first catalyst has a low positive gradient for the content of active phases, the second catalyst has a medium positive gradient and the third catalyst a high positive gradient. Groups of two single catalysts are preferred, !~
but in special cases up to four and more catalyst units can be connected in series.
The individual catalysts can be coated with active phases or active substances having identical or different compositions. This permits the optimum utilization of the ; ~
different effects of the individual catalysts, for example, ~ -with respect to both the starting temperature and the rate of reaction of deleterious substances.
Another modification, which is effective in the same direction, relates to a group of conventional monolithic-supported catalysts each of which has a uniform distributionof the content of active phases or active substances. At least two of these catalysts are connected in series in the direction of flow of the waste gases so that the rearward catalyst always has a content of active phases which is higher than that of the preceding catalyst. This arrangement also satisfies the condition of the invention, namely to provide an increasing content of active phases in the direction of flow of the waste gases and thus use a positive gradient for the content of active phases along the entire group. For example, a group comprising three monolithic catalysts thus provides a low concentration of active substances at the first catalyst a medium concentration at the second catalyst and a high concentration at the catalyst in the end position. However, within a discrete catalyst the active substance is uniformly distributed over the catalyst length.
In a modification of the invention the individual catalysts can also be coated with active phases having identical or different compositions of substances in order to obtain an optimum effect of the entire group.
When using a group of catalysts, two to four or more catalysts being feasible it depends on the individual case whether catalysts having different gradients for the content of active phases or two to four or more catalyst units having uniform coating with active substance are combined or whether according to a further modification of the invention the two types of catalyst, i.e., that according to the invention and a conventional catalyst, are combined.
The supported catalyst according to the invention or the catalyst groups according to the invention have the advan-tage that smaller amounts of active phases are rendered catalytically inactive due to loading with toxic agents because endurance tests on vehicles have shown that the catalyst poisons from fuel and oil are primarily deposited in the region of the waste gas inlet of the monolithic-supported catalysts, where ' they result in a substan-tially more intense deactivation than in ~he regions fur-ther downstream.
For the catalytic purification more active phase is available over a longer operating time since -the deactivation in the rear region of -the catalyst or of the yroups of catalysts is much slower and its extent is much smaller. The service life of the catalyst according to the invention is substantially longer than that of the known catalysts.
Moreover, according to the invention an increasing concentration of active phase in a direction towards the waste gas outlet of the catalyst or of the groups of catalysts has the advantage that as the concentration of combustible substances in the waste gas decreases and as the reaction thus becomes more difficult an increasing concentration of active substances is available which to some extent compensates for a decrease in the conversion and thus improves the overall efficiency of the catalyst.
The present invention will be further illustrated by way of the accompanying drawings in which, Figure 1 is a schematic of a monolithic-supported catalyst, according to one embodiment of the presen-t invention, disposed in a catalyst housing, Figure 2 is a graphic representation of feasible distri-bution curves for the content of active phases of the catalyst according to Figure 1 with a positive gradient, Figure 3 is a schematic of a group of three monolithic-supported catalysts according to another embodiment of the present invention, Figure 4 is a graphic representation of feasible distri-bution curves for the content of active phase of the catalysts of the group according to Figure 3 with positive gradlents, Figure 5 is a diagrammatic representation of a group ' according to a further embodiment of the present invention in which monolithic-supported catalysts are connected in series, each catalyst having a uniform distribution of the content of active phases in the direc~ion offlow of the waste gases.
Figure 6 is a diagrammatic representation of -the con-tents of active phase of -the individual monolithic catalysts according to Figure 5.
According to Figure 5 the ca-talyst portion 2 has a higher content of uniformly distributed active phase than that of the catalyst portion 1. The catalyst portion 3 has a higher content of uniformly distributed active phase than that of the catalyst portion 2.
The present invention will be further illustrated by way of the following Examples.
Example 1 A monolithic-supported catalyst produced by means of the dip-tank method and having a length of 150 mm is divided into 10 segments of 15 mm length in order to determine the content of active phase. The segments have the following content of platinum in % by weight:
segment 1 0.5 segment 2 0.28 segment 3 0.22 segment ~ 0.21 segment 5 0.20 segment 6 0.20 segment 7 0.21 segment 8 0.26 segment 9 0.28 segment 10 0.74 In a conversion test of this catalys-t in the fresh state the following results are obtained:
CO max. 98.04%
HC max. 77.33%
The results of the degree of conversion in % are obtained from the following equation:
100 x inlet concentration-outlet concentration inlet concentration E ample 2 The monolithic-supporte~ catalyst according to Example 1 is divided between the segments 5 and 6. ; ?
The two halves are so arranged in series in a device that the intersecting planes are pointing agalnst the direction of flow of the waste gases.
The conversion test of the fresh catalyst provided the following values: CO max. 98.0%, HC max. 78.71%.
The gradients (differences in content of Pt between the segments) in the direction of flow of the waste gases are:
+0.01% by weight/15 mm and +0.01% by weight/15 mm +0.01% by weight/15 mm +0.05% by weight/15 rmn +0.06% by weight/15 mrn +0.02% by weight/15 mm +0.22% by weight/15 mm +0.46% by weight/15 mm Over their entire length the two catalyst portions have a gradient of active phase of -~ 0.30%/75 mm and + 0.54%/75 mm.
_xample 3 A catalyst obtained according to Example 2 is aged for -~
100 hours at a waste gas temperature of 720C at the engine and is subsequently subjected to a conversion test. For CO max. and HC max. 98.04% and 74.74%, respectively, are obtained as degree of conversion. , The starting behaviour, which results from the ternperature ~ ;
at which predetermined amounts of conversion are attained, serves as a further measuring value for the quality of a catalyst for the purificakion of the waste gases from internal combustion engines. The higher the value obtained for the temperature the poorer will be the starting behaviour of the catalyst.
For the aged catalyst the following measured values for the starting behaviour were obtained:
50% CO - ~ 324C
90~ CO ~ 339C
50% HC ~ 336C
70% HC ~ 391C
Example 4 A monolithic-supported catalyst according to Example 1 is aged for 100 hours at a waste gas temperature of 720C
at the engine and then subjected to a conversion test. The values for CO max. and HC max. are 98.0~ and 71.35% respectively.
The starting behaviour is determined in the manner descrbied in Example 3.
The following measured data are obtained for the aged catalyst:
50% CO - ~ 325C
90% CO ~ 360C
50% HC - -~ 350C
70% HC ~ 437C
Thus, it is immediately evident from the Examples 3 and 4 that the catalyst according to the invention and the device according to the invention show improved ageing and starting behaviour.
Example 5 A monolithic-supported cordierite catalyst coated with active phase by means of the dip tank method according to the laid-open German Specification 2,306,395 and having a length of 150 mm is divided into 7 segments (each segment having a length of 21.4 mm) in order to determine the content of active phase. These segments have the following platinum contents in % by weight:
segment 1 0.185 segment 2 0.172 segment 3 0.170 segment 4 0.168 segment 5 0.172 segment 6 0.174 segment 7 0.21 ~ For the entire catalyst monolith, a platinum content of 1.65 g ~ 11 mg per mm is obtained. As is evident from the above values said platinum content is distributed over the ;
entire catalyst monolith in almost constant concentration. In the conversion test in the fresh state of the catalyst monolith the following values are obtained:
CO max. 99 %
HC max. 80.5%
Its starting behaviour is characteristic of this catalyst and is obtained from the temperatures at which 50 and ~, 90% CO as welI as 50 and 70% of HC are converted.
For the monolithic-supported catalyst according to - -example 5 the following values are obtained for the starting behaviour:
50% CO ~ 249C ~ .
90% CO ~ 283C
50% HC ~ 263C
70% HC - ~ 285C ~
Example 6 ~ -Two monolithic-supported catalysts coated differently with active phase by means of the dip tank method according to the laid-open German Specification 23 06 395 (each catalyst having a length o~ 75 mm) are divided into 4 segments (each segment having a length of 18.75 mm) in order to determine the ;~ ' conten-t of active phase. The following platinum contents are determined:
monolith 1 monolith 2 segment 1 0.197% by weiyht segment 1 0.252% by weight segment 2 0.193% by weight segment 2 0.252% by weight segment 3 0.194% by weight segment 3 0.249% by weight segment 4 0.210% by weight segment 4 0.253% by weight ~.
For the entire catalyst monoliths platinum contents .
of 0.6 g or 8.28 mg per mm of catalyst length and 0.9 g or 12.41 mg per mm of catalyst length are obtained.
The catalyst monoltihs 1 and 2 are so secured to a waste-gas purifying device that the catalyst monolith 1 is arranged in the direction of the flow of waste gases in front of the catalyst monolith 2.
In the conversion test in the fresh state the following values are obtained for the catalyst monoliths arranged in series:
CO max. 98%
HC max. 80%
For the starting behaviour the following temperatures are determined:
50gO CO - ~ 239C
90% CO 1 280C
50% HC - "~ 261C
70%O HC~ ~ 283C
_xample 7 ..
The monolith-supported catalyst according to Example 5 is aged for 100 hours at the engine and then subjected to a conversion test. The following values are obtained:
CO max. 98 %
HC max. 74.3%
For the starting behaviour the following temperatures are determined:
50% CO - -~ 343C
90% CO ---t 386C
50%~HC - ~ 360C
90% HC - -~ 404C
Example 8 The catalyst monoliths 1 and 2 arranged according to example 6 are aged for 100 hours at a waste gas temperature of 720C at the engine.
In the conversion test the following values are obtained.
CO max. 98 %
HC max. 77.5%
For the starting behaviour the following temperatures are determined:
50% CO ~ 332C
90~ CO ~ 355C
50% HC ~ 335C ~ ;
70% HC ~ 365C
It is clearly evident from the examples that in the device according to the invention the catalyst monoliths have a better conversion and starting behaviour and thus a better endurance test activi-ty after the ageing, despite the lower content of active phase. ~ ;
".~
.
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In the purification of waste gases from internal combustion engines in which the waste gases flow into contact with a monolithic-supported catalyst or group of mono-lithic-supported catalysts the improvement in which the catalyst or the group of catalysts has a continually increasing content of active phases in the direction of said flow of the waste gases, whereby said catalyst is less sensitive to inactivation due to loading with catalyst poisons contained in said waste gases.
2. A process according to claim 1, in which the content of active phases in the direction of flow of the waste gases has a positive gradient.
3. A process according to claim 1, in which at least two catalysts having continually different gradients for the content of active phases are connected in series in the direction of flow of the waste gases.
4. A process according to claim 3, in which the individual catalysts are coated with active phases having identical or different compositions of substances.
5. A process according to claim 1, 2 or 3, in which the waste gases flow in contact with a combination of one or more catalysts having a continually positive gradient for the content of active phases in the direction of flow of the waste gases and one or more catalysts having uniform distribution of the content of active phases.
6. In combination with an internal combustion engine a device including a monolithic supported catalyst or group of monolithic supported catalysts through which device waste gases from said internal combustion engine are arranged to flow in contact with said catalyst for the purification of said waste gases; said catalyst or group of catalysts having a continually increasing content of active phases in the direction of flow of said waste gases whereby said catalyst is less sensitive to inactivation due to loading with catalyst poisons in said waste gases.
7. The combination according to claim 6 in which the content of active phases in the direction of flow of the waste gases has a positive gradient.
8. The combination according to claim 6 in which at least two catalysts having continually different gradients for the content of active phases are connected in series in the direction of flow of the waste gases.
9. The combination according to claim 8 in which the individual catalysts are coated with active phases having identical or different compositions of substances.
10. The combination according to claim 6, 7, or 8 in which the waste gases are arranged to flow in contact with a combination of one or more catalysts having a continually positive gradient for the content of active phases in the direction of flow of the waste gases and one or more catalysts having uniform distribution of the content of active phases.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2542282.6 | 1975-09-23 | ||
| DE2542282A DE2542282C3 (en) | 1975-09-23 | 1975-09-23 | Monolithic supported catalytic converter for cleaning exhaust gases from internal combustion engines |
| DEP2554359.3 | 1975-12-03 | ||
| DE19752554359 DE2554359C2 (en) | 1975-12-03 | 1975-12-03 | Device for the catalytic cleaning of exhaust gases from internal combustion engines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081916A true CA1081916A (en) | 1980-07-22 |
Family
ID=25769431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA261,936A Expired CA1081916A (en) | 1975-09-23 | 1976-09-23 | Monolithic-supported catalyst or groups of monolithic- supported catalysts for the purification of waste gases of internal combustion engines |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4118199A (en) |
| JP (1) | JPS5256091A (en) |
| CA (1) | CA1081916A (en) |
| CS (1) | CS207368B2 (en) |
| ES (1) | ES451743A1 (en) |
| FR (1) | FR2325805A1 (en) |
| GB (1) | GB1554875A (en) |
| IT (1) | IT1070099B (en) |
| PL (1) | PL101655B1 (en) |
| SE (1) | SE429927B (en) |
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-
1976
- 1976-09-15 IT IT69243/76A patent/IT1070099B/en active
- 1976-09-16 CS CS766010A patent/CS207368B2/en unknown
- 1976-09-17 US US05/724,428 patent/US4118199A/en not_active Expired - Lifetime
- 1976-09-21 GB GB39060/76A patent/GB1554875A/en not_active Expired
- 1976-09-21 PL PL1976192549A patent/PL101655B1/en unknown
- 1976-09-22 FR FR7628518A patent/FR2325805A1/en active Granted
- 1976-09-22 ES ES451743A patent/ES451743A1/en not_active Expired
- 1976-09-23 CA CA261,936A patent/CA1081916A/en not_active Expired
- 1976-09-23 SE SE7610557A patent/SE429927B/en not_active IP Right Cessation
- 1976-09-24 JP JP51114565A patent/JPS5256091A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB1554875A (en) | 1979-10-31 |
| JPS5256091A (en) | 1977-05-09 |
| US4118199A (en) | 1978-10-03 |
| FR2325805A1 (en) | 1977-04-22 |
| ES451743A1 (en) | 1977-09-16 |
| PL101655B1 (en) | 1979-01-31 |
| IT1070099B (en) | 1985-03-25 |
| SE429927B (en) | 1983-10-10 |
| SE7610557L (en) | 1977-03-24 |
| CS207368B2 (en) | 1981-07-31 |
| FR2325805B1 (en) | 1978-10-20 |
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