DE2246377A1 - CATALYST TO REMOVE AIR POLLUTION - Google Patents

Description

PATENT ADVOCATE OFFICE Frankfurt / M .: Thomsen TiEDTKE ■ - i Dipl.-Ing. W. Weinkauff
(Fuchshohl 71) TEL. (0811) 53 0211 TELEX:
63 0212 5-24 303 topat PAT
Munich: Dipl.-Chem. I.
Dipl.-Ing. H.
Dipl.-Chem.
Dipl.-Ing. R.
Dipl.-Chem. 22A6377 SüHLING E N T A N * Dr. D. Thomsen
Tiedtke
G. Buehling
Chins
Dr. U. Eggers

800Q Munich 2

Kaiser-Ludwig-Platz6 September 21, 1972

Nissan Motor Company, Limited Yokohama City (Japan)

Catalyst for removing air pollution

The invention relates to a catalyst which is useful for removing air pollutants from exhaust gases from a variety of industrial plants and exhausted from automotive internal combustion engines. The invention also relates to a method of manufacture such a catalyst.

The exhaust gases from industrial plants and automotive internal combustion engines contain hydrocarbons and carbon monoxide, which result from partial or incomplete combustion of the fuel, as well as nitrogen oxides, which are produced by reaction between the oxygen and nitrogen gases of the air at elevated temperatures. For

Verbal agreements, especially by telephone, require written confirmation 309826/1022 Postal check (Munich) account 116874 Dresdner Bank (Munich) account

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prevention of air pollution caused by the emission of this toxic compounds, efforts have been made to render the exhaust gases harmless do by further oxidizing the unburned hydrocarbons and carbon monoxide in the exhaust gases and the Nitrogen oxides reduced or decomposed before the exhaust gases in the free air can be vented. One of these efforts is to use a catalyst that does this is designed to remove the toxic compounds through contact reactions, which are expressed as follows can i

2CO ■ * · O ₂ - ♦ 2CO ₂ ,

kC H + (ΊΗ + n) 0 " · 4mC0 + 2nJl 0,

mn. <J ~ ^Λ

2NO + 2yC0 ψ xN _g + 2yCQ ₂ and

^2N x ° y ~ * ^XN 2 * ^y0 2 '

where m, η, χ and y are integers which are appropriately ge can be given.

Where the catalyst designed to achieve these purposes, especially in internal combustion engines of motor vehicles is used, the catalyst should meet the following requirements

(1) Sufficient durability to ensure optimal reactivity to oxidation or reduction of the toxic

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Connections for an extended service life of the catalytic converter.

(2) low temperature activity, namely the ability to to be effective at relatively low temperatures.

(3) Satisfactory conversion efficiency for oxidizing the combustible compounds in a temperature range from about 100 to 900 ° C.

(4) Sufficient mechanical strength, in particular abrasion resistance, to withstand impacts and vibrations in to withstand the working position.

(5) Minimized resistance to the flow of exhaust gases through the catalytic converter.

The usual catalysts in the form of pellets or tablets meet the above requirements (2), (4) and (5) are not satisfactorily fair. The requirements are all taken into account by one Catalyst in the form of a block, which in terms of volume has the extent of tenths of a liter to liters and which has a number of passages extending in one or two directions. The catalyst in block form of this type is hereinafter referred to as "monolithic catalyst" and typically comprises a catalyst with honeycomb structure. In contrast to such a monolithic catalyst, the catalyst is in pellet

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or tablet form as a "non-monolithic catalyst" designated. The monolithic catalyst is thus considered to conform to air pollution control arrangements in automobiles, although the non-monolithic catalyst is for use in treating exhaust gases from a variety of industrial plants and equipment is acceptable.

The monolithic catalyst can be prepared using the following three different methods:

a. A mixture of catalyst and carrier substances is first prepared by mixing or precipitating them. The mixture is then shaped into a coherent block, which is then sintered.

b. First is a catalyst material on a coherent Supported, for example by means of a deposition method, with the catalyst on the support is deposited. The carrier, which thus carries the catalyst substance, is then sintered and forms a monolithic catalyst block.

c. First, a catalyst material is impregnated on a coherent carrier and the Carrier, which thus carries the catalyst material, becomes sintered with a monolithic catalyst.

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The "monolithic carrier" mentioned here is intended to be a Define a special type of carrier, which is in the form of a block, from tenths of a liter to Li- * tern and which have a number of passages extending in one or two directions, similar to that monolithic catalyst defined above. The definition of "non-monolithic beam" as given here should be mentioned, is self-evident from the definition of the non-monolithic catalyst.

Of the three different methods described above, methods are a. and b. with different too solving technical problems and as such are presently unacceptable for practical applications considered. To implement the method according to the invention therefore method c. assumed which is easily and economically feasible and is trained to to produce a catalyst with sufficient effectiveness and durability.

For the purpose of removing air pollutants from exhaust gases from internal combustion engines in motor vehicles A wide variety of catalysts are currently available. This includes a group of catalysts, which copper oxides and chromium oxides in the absence or presence of

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Palladium containing (disclosed in published Japanese Patent Applications 39-19781, 39-30148 and 44-11780) and a group of catalysts "which manganese oxides in the presence of palladium _f copper oxides, iron oxides and Chromoxyden contain (disclosed in Japanese Patent Applications 40-8322, 40-24366, 42-5324 and 42-15717). However, these catalysts are not entirely acceptable because those of the former group exhibit poor durability because of the copper oxides contained therein, and the catalysts of the latter group tend to be ineffective at relatively low temperatures. A limited number of catalysts containing nickel oxides have also been proposed. These include a group of catalysts containing nickel oxides and chromium oxides (disclosed in Japanese patent application 46-7572) and a group of catalysts containing nickel oxides, chromium oxides and barium oxides (disclosed in Japanese patent application 45-365 * 7, however, it is emphasized that virtually none of these catalysts have been able to function satisfactorily at low temperatures. Thus, there is a need for catalysts having sufficient durability and efficiency at low temperatures, which are particularly required where the catalysts are used in air pollution control devices of vehicle internal combustion engines should be.

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It has now surprisingly been found that one Masser which a nickel oxide, a chromium oxide and metallic Contains palladium, is satisfactorily effective at low temperatures and is sufficiently durable when removed for removal of air pollution from exhaust gases from industrial plants and equipment and internal combustion engines for automobiles takes into use. The increased low temperature effectiveness and durability of the catalyst, which has the composition noted above, cannot at present be comprehensively assessed. However, one hypothesis is given below. The palladium that is in the catalyst is highly effective in oxidizing hydrocarbons and carbon monoxide, and has a remarkable one high durability. Chromium oxide, which is available in different Forms as oxide is considerably effective in the oxidation of hydrocarbons. on the other hand Nickel oxide contributes to the stabilization of the chromium oxide. The catalyst in its entirety therefore shows a high Durability and low temperature effectiveness.

Experiments have been carried out to the invention Catalyst preferred concentration ranges of nickel, Determine chromium and palladium. The experiments have shown that acceptable results are achieved if the catalyst consists of a total of 0.1 to 3.5 mol of nickel and chromium, and min-

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There is at least 0.0003 NoI palladium per 1 liter of carrier. To the Prepare such a catalyst by impregnating a support with the catalyst material, a total of 0.1 should be up to 3.5 moles of nickel and chromium and at least 0.0003 moles of palladium in the form of metal salts first in 1 liter of carrier followed by sintering the carrier and catalyst in a stream of air.

The concentrations of nickel and chromium like them above are important. If the concentrations are just under 0.1 mol per 1 liter of carrier, then the will not be Catalyst its effectiveness on air pollution. On the other hand, if the carrier of the same volume is impregnated with less than 3.5 moles of nickel and chromium, not only is the activity of the catalyst likely to decrease as a result of the degraded surface area, but that Metal powder of nickel and chromium, which is incompletely carried on the support, tends to go with the flow of the exhaust gases to be carried away and emptied into the open air and thus forms a source of pollution in the air Heavy metals.

The molar ratio between nickel and chromium should be considered in consideration of the desired effectiveness and durability of the catalyst preferably in the range from 1: 6 to 6: 1

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lie. The greater or lesser molar ratio than these ranges would result in an inability of the nickel or chromium lead to show specific properties because of the lack of nickel or chromium.

Furthermore, if less than 0.0003 moles of palladium on the If the carrier is supported, the catalyst will not be effective, especially on carbon monoxide. The effectiveness of the catalyst increases with the increase in the concentration of the palladium above this particular level and therefore the higher the palladium concentration, the more effective the catalyst is * The concentration of palladium can but in the range up to 0.1 moles per 1 liter of practical carrier There are reasons, especially from an economic point of view.

In order to have available catalysts with further improved durability, further development work has been carried out carried out by adding various kinds of metal oxides to the catalyst of the nature described above. It has been shown that extremely high durability can be achieved when one uses the oxides of nickel, chromium and palladium, one or more oxides of zirconium, bismuth and vanadium and aluminum are added. Such durability improvement can be present

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cannot yet be accurately assessed. There were attempts carried out in order to determine the preferred proportions of these additives to the amounts of nickel and chromium oxides. the Experiments have led to the finding that the total concentration in moles of the metal components of those mentioned above Additions amount to about 1/25 to 1/4 of the total molar concentration of the metal components of nickel and chromium oxides should, if an aluminum oxide is to be included in the additives, and should be about 1/50 to 1/5 »if the aluminum oxide is not to be included in the additives. The molar concentrations of the additives can be varied within these ranges regardless of the number and types of the selected additives. However, if the additives are used in a concentration which is lower than that If the specified lower limit is specified, the intended effect of the additives, namely the desired durability of the catalyst, is not achieved. On the other hand, if the additions in at a concentration higher than the specified upper limit, the catalyst would not exhibit the desired low temperature performance, though the durability of the catalyst would be increased.

The catalyst, which is prepared in the manner described above, consists essentially of 1 liter Carrier impregnated with nickel and chromium oxides in one content

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a total of 0.1 to 3.5 mole of metal components and in a ratio of about 1: 6 to 6S l -a _{f ra} palladium oxide in a content of 0.0003 to 0.1 mole of metal component; and one or more oxides of zirconium, bismuth, vanadium and aluminum in a content of metal components in total molar concentrations of 1/25 to 1/4 or 1/50 to 1/4 of the total molar concentrations of the metal components of the nickel and chromium oxides in the presence of fozw "in the absence of the aluminum oxide in i @ n.

The palladium, which plays an important role in the catalyst according to the invention, is not only expensive, but, as is well known, seldom also with regard to its natural occurrence. To a substantial reduction in quantity of palladium without deteriorating low temperature efficiency and durability of the catalyst, investigations have been made by adding various ones Substances to the catalyst, which from the oxides of nickel, chromium and palladium in those specified above There is quantitative proportions. Thus it has been found that such a purpose can be achieved by going to the nickel, Chromium and palladium oxides copper oxide added, which is particularly active for carbon monoxide oxidation. Catalysts containing copper oxide are generally known for that they have poor durability, but in the event

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of the catalyst with the composition described above, the copper oxide is sufficiently stabilized by the nickel oxide which is also present. The catalyst in its entirety therefore has a satisfactory durability. However, since the durability of the catalyst would be reduced if the amount of copper oxide in the catalyst was excessively large Amount, it is necessary to keep the concentration of copper oxide within a certain range restrict. According to the experiments carried out, such a range should be determined in such a way that the Metal component of copper oxide has a molar concentration of about 1/20 to 1/3 of the total molar concentration which has metal components of nickel and chromium oxides. Incorporation of copper in the catalyst in an amount which is less than the specified lower limit would result in the intended effect of the copper oxide, namely the reduction in the amount used Palladium, is not achieved, while the use of copper in an amount which is greater than that specified upper limit would lead to a critical deterioration in the durability of the resulting catalyst, although the low temperature efficiency of the catalyst would be increased.

The catalyst prepared in this way consists essentially of 309826/10 ??

from 1 liter carrier, impregnated with nickel and chromium oxides in a total content of 0.1 to 3.5 mol of metal components, palladium oxide in a content of 0.0003 to 0.1 mol Palladium as metal, and copper oxide as metal component in a concentration of 1/20 to 1/3 of the total molar Concentration of the metal components of nickel and chromium oxides.

The durability of the catalyst, which is made up of the oxides of nickel, chromium, palladium and copper can be further improved by adding one or more of the oxides of zirconium, bismuth, vanadium and aluminum, as described above. It It is important that these additives are present in the catalyst in such an amount that the total molar concentration of the metal components of the additives in the range from 1/25 to 1/4 of the total molar concentration of the metal components the nickel, chromium and copper oxides are, if an aluminum oxide is to be included in the additives, and in the range from 1/50 to 1/5, if aluminum oxide should not be included in the additives. The catalyst prepared in this way consists essentially of 1 liter of carrier, impregnated with nickel and chromium oxides in a total content of 0.1 to 3.5 moles of metal components in a molar ratio of 1: 6 to 6: 1; Palladium oxide in a content of 0.0003 to 0.1 mol

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Metal component; Copper oxide in a metal component content of a molar concentration of 1/2 to 1/8 of the total molar concentration of the metal components of the nickel and chromium oxides, and one or more of zirconium, bismuth, vanadium and aluminum in a metal component content of a molar concentration of 1 / 25 to 1/4 or /. l / 50 to 1/5 of the total molar concentration of the metal components of the nickel, chromium and copper oxides in the presence or absence of the aluminum oxide in the additives.

The preferred support materials useful in the catalyst of the present invention can be any refractory materials including clays, silica-magnesia, and Japanese oxidized acidic clay. The carrier can be monolithic or non-monolithic as defined above. Where the monolithic support is used, it can be formed from a material containing an aluminum oxide such as cordierite, β-spodumene and alpha-aluminum oxide. Where on the other hand the non-monolithic carrier type for example, is preferably in the form of pellets or tablets, these may be formed from a material which an alumina such as alpha-alumina, ^. "- contains aluminum oxide, C -Aluminiumoxyd and chi-Aluminii oxide If desired, the one mentioned above

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Codierite, ß-spodumene or alpha-aluminum oxide formed monolithic carriers can be improved in such a way that a activated aluminum oxide, for example £ f-aluminum oxide and <Jf -alumina, on the surface of the base material is deposited. For the sake of simplicity, the support of this particular type is hereinafter referred to as "alumina deposited" monolithic carrier ".

The more precise nature of the catalyst of the invention and the advantages of the catalytic converter over its prior art counterparts emerges more precisely from the following Ausf ührt-ngsbeispielen the invention and by comparison between these examples and some samples which have been conventionally prepared. The adjacent Drawing illustrates a graph showing the relationship between the (to be defined later) Conversion efficiency of carbon monoxide, propane and nitrogen monoxide and the temperature.

example 1

1 liter of a granular carrier, trelcher out commercially available activated γ-alumina of about 6 to 8 meshes per 6.45 cm (= 1 square inch) to 1.35 liters of an aqueous solution of a mixture of

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Nickel nitrate added chromium nitrate and palladium nitrate, with 0.67 moles of nickel ions, 2.7 moles of chromium ions and 0.011 moles Palladium ions are contained in 1 liter of the solution. The carrier so impregnated with the nitrates of nickel, chromium and palladium is removed from the solution for 15 hours at dried at a temperature of 120 ° C and then sintered in a stream of air for 3 hours at a temperature of 750 ° C. Of the The resulting catalyst contains metal oxides in which 0.3 moles of nickel, 1.2 moles of chromium and 0.005 moles of palladium are present as metals in 1 liter of catalyst.

ι,

Example 2

1 liter of granular carrier, which: consists of the same aluminum oxide as used in Example 1 is added to 1.35 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 1.7 moles of nickel ions, 1.7 moles of chromium ions and 0.011 mol of palladium ions are contained in 1 liter of solution and are impregnated therewith. Upon completion of the impregnation, the carrier is removed from the solution and then dried and sinters under the same conditions as in Example 1. 1 liter of the catalyst prepared in this way contains metal oxides in which 0.75 mol of nickel, 0.75 mol of chromium and 0.005 mol Palladium as metals are present.

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Example 3

1 liter of a granular carrier made of the same material as in Example 1 becomes 1.50 Liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate added, with 2.7 Hol Nickel ions, 0.67 moles of chromium ions and 0.011 moles of palladium ions are contained in 1 liter of the solution. The one with the nitrates The support impregnated with the nickel, chromium and palladium is removed from the solution, dried and under the same conditions sintered as in Example 1. 1 liter of the catalyst prepared in this way contains metal oxides in which 1.2 mol nickel, 0.3 mol chromium and 0.005 mol palladium * as metals, are present.

Example 4

1 liter of a granular carrier, which consists of commercially available activated chi-aluminum oxide of about 6 to 8 meshes per 6.45 cm ² , is added to 1.50 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, where 1 , 5 moles of nickel ions, 1.5 moles of chromium ions and 0.010 moles of palladium ions are contained in 1 liter of solution. The carrier so impregnated with the nitrates of nickel, chromium and palladium is made of

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the solution removed, 15 hours at a temperature of Dried at 120 ° C and sintered in a stream of air for 5 hours at a temperature of 700 ° C. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 Moles of chromium and 0.005 moles of palladium as metals in 1 liter of the Catalyst are included.

Example 5

1 liter of a granular carrier, which is made of a commercially available activated <S -aluminum oxide, is extrusion-deformed to a diameter of about 3 mm and made into 1.20 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate added, with 1.9 mol nickel ions, 1.9 mol chromium ions and 0.013 mol Palladium ions are present in 1 liter of the solution. The support impregnated in this way with the nitrates of nickel, chromium and palladium is removed from the solution, dried for 15 hours at a temperature of 120 ° C. and in a stream of air Sintered for 3 hours at a temperature of 750 ° C. Which resulting catalyst contains metal oxides, in 'elclEno, 7 5 moles of nickel, 0.75 mol of chromium and 0.005 mol of palladium are present as metals in 1 liter of catalyst.

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Example 6

1 liter of a granular carrier, which consists of the same activated alumina as used in Example 5, is added to 1.20 liters of an aqueous solution of a mixture containing 1.0 mol of nickel ions, 2.8 mol of chromium ions and 0.013 mol of palladium ions , present in 1 liter of the solution. The carrier impregnated with the nitrates of nickel, chromium and palladium is removed from the solution, dried for 15 hours at a temperature of 120 ° C. and sintered in a stream of air for 3 hours at a temperature of 750 ° C. The resulting catalyst contains metal oxides in which there are no mol of nickel, 1.1 mol of chromium and 0.005 mol of palladium as metals in 1 liter of catalyst.

Example 7

1 liter of a granular carrier, which consists of the same aluminum oxide as used in Example 5 becomes 1.20 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate added, with 2.8 mol of nickel ions, 1.0 mol of chromium ions and 0.013 mol of palladium ions in 1 liter of the solution are. The one with the nitrates of nickel, chrome and

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Palladium-impregnated carrier is removed from the solution and dried under the same conditions as in Example 6 and sintered. The resulting catalyst contains metal oxides, in soft 1, IMo 1 nickel, 0.4 mol chromium and 0.005 Moles of palladium are present as metals in 1 liter of the catalyst.

Example 8

1 liter of a granule-shaped carrier, which is made of commercially available alpha-aluminum oxide of about 8 meshes in 6.45 ent becomes 1.20 liters of an aqueous solution a mixture of Mickeine Nitrate, Chromium Nitrate and Palladium Nitrate added, 1.5 moles of nickel ions, 1.5 moles of chromium ions and 0.020 moles of palladium ions being present in 1 liter of solution are. The carrier impregnated with the nitrates of nickel, chromium and palladium in this way is removed from the solution, Dried for 15 hours at a temperature of 120 ° C and sintered in a stream of air for 3 hours at a temperature of 800 ° C. The catalyst obtained in this way contains metal oxides, in which Ci ^ 6 moles of nickel, 0.6 moles of chromium and 0.008 moles of palladium as metals are present in 1 liter of the catalyst.

Example 9

1 liter of a granular carrier consisting of 309826/1022

commercially available activated gamma-alumina of about 6 to 8 meshes in 6.45 cm, is added to 1.35 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 1.7 hol nickel ions, 1.7 hol Chromium ions and 0.0022 moles of palladium ions are present in 1 liter of the solution. The carrier impregnated in this way with the nitrates of nickel, chromium and palladium is removed from the solution, dried for 15 hours at a temperature of 120.degree. C. and sintered in a stream of air for 3 hours at a temperature of 750.degree. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles of chromium and 0.001% of palladium are present as metals in 1 liter of catalyst .

Example 10

A monolithic block girder made of cordlerite, which the volume of 0.785 liters is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, Chromium nitrate and palladium nitrate are immersed, with 1.5 moles of nickel ions, 1.5 moles of chromium ions and 0.041 moles of palladium ions are present in 1 liter of the solution. So impregnated with the nitrates of nickel, chromium and palladium Carrier is removed from the solution, dried for 18 hours at a temperature of 120 ° C. and in a stream of air

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sintered at a temperature of 75o ° C for 5 hours. The resulting monolithic catalyst, which has an overall volume of ο, 785 liters, contains metal oxides in which o, 3 mol Nickel, 0.3 hol chromium and 0.008 hol palladium are present as metals.

Example Il

A monolithic block carrier made of ß-spodumene with a volume of 0.785 liters is made in 3.0 liters immersed in an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, with 1.9 moles of nickel ions, 1.9 moles of chromium ions and 0.051 moles of palladium ions in 1 liter of solution are present. The carrier thus impregnated with the metal nitrates is treated under the same conditions as processed in example 10. The monolithic catalyst obtained in this way contains metal oxides in which o, 3 mol Nickel, 0.3 mol of chromium and 0.008 mol of palladium are present as metals.

Example 12

A monolithic cordierite block girder, which which has a volume of 0.785 liters, is immersed in a commercially available aluminum oxide sol. The carrier

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is sintered at a temperature of 7OO ° C then for 3 hours, wherein gamma alumina is deposited on ä @ m carrier. The same process is repeated three times, so that a total of 21% by weight of gamma aluminum oxide is finally deposited on the continuous cordierite support. The aluminum oxide-deposited monolithic support obtained in this way is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 0.55 moles of nickel ions, 1.7 moles of chromium ions and 0.018 moles of palladium ions being present in 1 liter of solution, The carrier impregnated in this way with the nitrates of nickel, chromium and palladium is removed from the solution * 18 hours at a temperature of 120 ° C and dried in eii5 - ^. Air flow for 5 hours at a temperature of 750 ° C as in Example 10, sintered aluminum oxide-deposited moaolithic catalyst contains metal oxides in which Q "15 moles of nickel> 0.45 moles of chromium and 0.005 moles of palladium are present as metals *

- Example "13

An alumina-deposited monolithic carrier is first prepared in the same manner as in Example 12 prepares. The carrier, which so the voluminous Äfflesstmgen of 0.785 liters, 3.0 liters becomes one

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immersed aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 1.1 moles of nickel ions, 1.1 moles of chromium ions and 0.018 moles of palladium ions in 1 liter of solution are present. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example. The resulting monolithic catalyst contains metal oxides in which 0.3 moles of nickel, 0.3 moles of chromium and 0.005 moles of palladium are present as metals.

Example 14

An alumina-deposited monolithic carrier is first prepared in the same manner as in Example 12. The carrier, which has the volume dimension of 0.785 liters, is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 1.6 mol of nickel ions, 0.55 mol of chromium ions and 0.018 mol of palladium ions in 1 Liters of solution are present. The support impregnated in this way with the nitrates of nickel, chromium and palladium is removed from the solution, dried for 18 hours at a temperature of 120 ° C. and sintered in a stream of air for 5 hours at a temperature of 750 ° C. The resulting monolithic catalyst contains metal oxides in which o.45 moles of winding,

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Ο, 15 moles of chromium and 0 * 005 moles of palladium * as metal®, are.'

Example 15

A Aluminiuraoxyä-deposited monolithic carrier, which was prepared in the same manner as in Example 12, in 3, O liters of an aqueous solution of a mixture of Nick Eini would apply _f chromium nitrate and palladium nitrate immersed, wherein 1.1 mol Niekelionen, 1.1 mol Chroiaionen and 0.0037 moles of palladium ions are present in 1 liter of the solution. The support impregnated with the nitrates of nickel, chromium and palladium is removed from the solution, ^{dried for 18 hours at a temperature of 120 °} C. and sintered for 5 hours in a stream of air at a temperature of 750 ° C. The monolithic catalyst obtained in this way contains metal oxides in which Q _# 3 mol nickel, 0.3 mol chromium and 0.001 mol palladium are present as metals »

Example 16

A monolithic carrier made of ß-spodumene, which the volumetric extent of 0.785 liters ^ is in an im Commercially available alumina sol immersed and then sintered for 3 hours at a temperature of 700 C, so that

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gamma aluminum oxide is deposited on the carrier. The same process is repeated three times, so that a total of 25 % by weight of gamma aluminum oxide are finally deposited on the ß-spodumene carrier. The monolithic support obtained in this catfish is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and palladium nitrate, 1.3 moles of nickel ions, 1.3 moles of chromium ions and 0.021 moles of palladium ions being present in 1 liter of the solution . The carrier thus impregnated with metal nitrates of nickel, chromium and palladium is removed and dried and sintered in the same way as in Example 15. The resulting monolithic catalyst contains metal oxides in which 0.3 moles of nickel, 0.3 moles of chromium and 0.005 moles of palladium are present as metals.

Example 17

One liter of a carrier, which was formed by extrusion molding of commercially available activated granulated delta-aluminum oxide and has a diameter of about 3 mm, is immersed in 1.20 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and zirconyl nitrate, 1.9 Mol of nickel ions, 1.9 mol of chromium ions, 0.013 mol of palladium ions and 0.38 mol of zirconium ions are present in 1 liter of solution. The one with the nitrates of

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Nickel, chromium, palladium and sirkon impregnated substrates is removed from the solution, dried for 15 hours at a temperature of 120 ° C and 3 hours in a stream of air at sintered at a temperature of 750 ° C »The resulting Carrier contains metal oxides, in wektai c * 75 mol nickel, 0.75 mol Chromium, 0.005 mole palladium and 0.15 mole zirconium as metals are present in one liter of the catalyst.

Example 18

One liter of an extrusion buckled support mm of diameter 3 of a commercially available activated granular delta alumina, a mixture of nickel nitrate, chromium nitrate, palladium nitrate and ZirkonyInitrat is set as I ₉ 20.Litern an aqueous solution added to _s with 1.9 mole of nickel ions, 1.9 moles of chromium ions, 0.013 moles of palladium ions and 0.13 moles of zirconium ions are present in 1 liter of the solution. The carrier thus obtained is removed from the solution and dried and sintered in the same manner as in Example 17. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles of chromium, 0.005 moles of palladium and 0.05 moles of zirconium are present as metals in one liter of the catalyst.

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Example 19

A monolithic cordierite carrier softens that Has a volume dimension of 0.785 liters, is sold in a available alumina sol immersed. The carrier is then sintered for three hours at a temperature of 700 ° C, so that gamma-aluminum oxide is deposited on the carrier. The same process is repeated three times for a total of 21% by weight of gamma aluminum oxide are finally deposited on the cordierite carrier. The alumina-deposited one monolithic support, which is obtained in this way »is composed of 3.0 liters of an aqueous solution of a mixture Nickel nitrate, chromium nitrate, palladium nitrate and zirconium nitrate immersed, with 1.1 moles of nickel ions, 1.1 moles of chromium nitrate, 0.018 moles of palladium nitrate and 0.18 moles of zirconium nitrate being present are. The carrier is then removed from the solution, dried for 15 hours at a temperature of 120 ° C. and in a Air flow sintered for 6 hours at a temperature of 750 ° C. The resulting monolithic catalyst contains metal oxides in which 0.3 moles of nickel, 0.3 moles of chromium, 0.005 moles of palladium and 0.05 moles of zirconium are present as metals.

Example 20 An alumina-deposited monolithic carrier,

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which was prepared in the same manner as in Example 19 is dissolved in 3.0 liters of an aqueous solution of a mixture immersed in nickel nitrate, chromium nitrate, palladium nitrate and zirconyl nitrate, with 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.018 moles of palladium ions, and 0.073 moles of zirconium ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered in the same manner as in Example 19. The monolithic catalyst obtained in this way contains 0.3 mol of nickel, 0.3 moles of chromium, 0.005 moles of palladium and 0.02 moles of zirconium as Metals calculated, present.

Example 21 One liter of a granular carrier which

made of commercially available activated gamma aluminum oxide from

2 about 6 to 8 stitches per 6.45 cm is formed 1.35 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and bismuth nitrate are added, 1.7 mol nickel ions, 1.7 mol chromium ions, 0.011 Moles of palladium ions and 0.27 moles of bismuth ions are present in 1 liter of solution. The one with the nitrates of nickel, chromium, Palladium and bismuth impregnated carrier is removed from the solution, dried for 15 hours at a temperature of 120 ° C. and sintered in a stream of air for 3 hours at a temperature of 750 ° C. The resulting catalyst contains metal oxides in which 0.7.5 moles of nickel, 0.75 moles of chromium,

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0.05 moles of palladium and 0.12 moles of bismuth as metals in one Liters of catalyst are present.

Example 22

1 liter of a vehicle of the same type »as he in Example 21 was used, is added to 1.35 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, Palladium nitrate and bismuth nitrate are added, 1.7 moles of nickel ions, 1.7 moles of chromium ions, 0.011 moles of palladium ions and 0.11 moles of bismuth ions being present in 1 liter of solution. The carrier is dried and sintered under the same conditions as in Example 21. The resulting catalyst contains metal oxides in which 0.75 moles of nickel >> 0.75 Moles of chromium, 0.005 moles of palladium and 0.05 moles of bismuth al · metals are present in 1 liter of catalyst.

Example 23

A monolithic support, which was formed by extrusion molding of cordierite and which has a small volume Dimensions of 0.785 liters is sold in a available alumina sol immersed. The carrier is then sintered at a temperature of 700 ° C. for 3 hours, with Garama aluminum oxide being deposited on the carrier.

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The same process is repeated three times, making a total Finally, 21% by weight of gamma aluminum oxide on the cordierite support * The alumina-deposited monolithic support obtained in this way, is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and bismuth nitrate immersed, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.018 moles of palladium ions and 0.18 moles of bismuth ions in 1 liter of solution are present. The carrier impregnated with the nitrates of nickel, chromium, palladium and bismuth is removed from the solution, dried for 15 hours at a temperature of 120 ° C and 6 hours in a stream of air at sintered at a temperature of 750 ° C. The resulting alumina-deposited monolithic catalyst contains metal oxides, in which 0.3 moles of nickel, 0.3 moles of chromium, O, OO5 Moles of palladium and 0.05 moles of bismuth are present as metals.

Example 24

An alumina-deposited monolithic support of the same kind and dimension as used in Example 23 is placed in 3.0 liters of an aqueous solution Mixture of nickel nitrate, chromium nitrate, palladium nitrate and bismuth nitrate immersed, with 1.1 mol. Nickel ions, 1.1 mol Chromium ions, 0.018 moles palladium ions and 0.073 moles bismuth ions

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are present in one liter of the solution. The carrier is removed from the solution and dried and sintered under the same conditions as in Example 23. The resulting

¹ I.

Contains alumina-deposited monolithic catalyst Metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.005 mol of palladium and 0.02 mol of bismuth are present as metals.

Example 25

One liter of an extrusion-molded support made of commercially available activated delta-aluminum oxide with a diameter of 3 mm is immersed in 1.20 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and vanadium nitrate, with 1.9 moles of nickel ions, 1.9 Moles of chromium ions, 0.013 moles of palladium ions and 0.38 moles of vanadium ions are present in 1 liter of solution. The carrier impregnated in this way with the nitrates of nickel, chromium, palladium and vanadium is removed from the solution, after which it is ^{dried for 15 hours at a temperature of 120 °} C. and sintered for 3 hours in a stream of air at a temperature of 750 C. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles of chromium, 0.005 moles of palladium and 0.15 moles of vanadium, as metals, are present in one liter of catalyst.

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Example 26

An alumina-deposited monolithic support, which is similar to that used in Example 25, is dissolved in 1.20 liters of an aqueous solution of a mixture of nickel nitrate, Chromium nitrate, palladium nitrate and vanadium nitrate immersed, with 1.9 moles of nickel ions, 1.9 moles of chromium ions, 0.013 Moles of palladium ions and 0.13 moles of vanadium ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example 25. The resulting monolithic catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles of chromium, 0.005 moles of palladium and 0.05 moles of vanadium are used as metals are present in one liter of the catalyst.

Example 27

A monolithic carrier made of ß-spodumene with the volumetric extent of 0.785 liters is converted into a commercially available one Immersed aluminum oxide sol and then sintered for 3 hours at a temperature of 700 C, so that gamma-aluminum oxide is deposited on the carrier. The same procedure is repeated three times, so that a total of 25 wt.% gamma aluminum oxide deposited on the ß-spodumene carrier will. The alumina-deposited monolithic carrier made in this way is 3.0 liters

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immersed in an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and vanadium nitrate, wherein 1.3 mol of nickel ions, 1.3 mol of chromium ions, 0.018 mol of palladium ions and 0.21 mol of vanadium ions are present in 1 liter of solution are. The carrier is then removed from the solution, dried for 15 hours at a temperature of 120 ° C. and sintered 6 hours in a stream of air at a temperature of 750 ° C. The alumina-deposited monolithic catalyst which was obtained in this way contains metal oxides in which O, 3 Mol of nickel, 0.3 mol of nickel, 0.3 mol of chromium, 0.005 mol of palladium and 0.05 mol of vanadium are present as metals.

Example 28

An alumina-deposited monolithic carrier, which was prepared in the same manner as in Example 27, is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate / chromium nitrate, palladium nitrate and Vanadium nitrate immersed, with 1.3 moles of nickel ions, 1.3 moles of chromium ions, 0.018 moles of palladium ions and 0.085 moles of vanadium ions in 1 liter of solution. Removed the carrier one then out of the solution and dried and sintered it under the same conditions as in Example 27. The on this Alumina-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 moles of chromium, 0.005 moles of palladium and 0.02 moles of vanadium as

1022

Metals are present.

Example 29

One liter of a granular carrier made from commercially available activated chi-alumina from consists of about 6 to 8 stitches per 6.45 cm, becomes 1.50 liters each aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and aluminum nitrate added, where 1.5 moles of nickel ions, 1.5 moles of chromium ions, 0.010 Moles of palladium ions and 0.40 moles of aluminum ions are present in 1 liter of solution. The one with the nitrates of nickel » Chromium, palladium and aluminum impregnated support is removed from the solution for 15 hours at a temperature of Dried at 120 ° C and sintered for 3 hours in a stream of air at a temperature of 750 ° C. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles Chromium, 0.005 mol of palladium and 0.20 mol of aluminum are present as metals in 1 liter of the catalyst.

Example 30

One liter of a granular carrier made of the same material as used in Example 29 becomes 1.5 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and aluminum nitrate added, where 1.5 mol nickel ionsj 1.5 mol

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■ «36 -

Chromium ions, 0 _f 010 moles of palladium ions and 0.10 moles of aluminum ions are present in 1 liter of the solution. The support is then removed from the solution and dried and sintered under the same conditions as in Example 29. The resulting catalyst contains metal oxides in which 0.75 moles of nickel, 0.75 moles of chromium, 0.005 moles of palladium and 0.05 moles Moles of aluminum are present as metals in 1 liter of catalyst.

Example 31

A monolithic carrier made of ß-spodumene with a volume of 0.785 liters is immersed in a commercially available aluminum oxide sol and then for 3 hours sintered at a temperature of 700 ° C, so that gamma-aluminum oxide is deposited on the carrier. The same work cycle is repeated three times, resulting in a total of 25% by weight gamma aluminum oxide deposited on the ß-spodumene carrier will. The alumina-deposited monolithic carrier prepared in this way is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and aluminum nitrate, 1.3 mol Nickel ions, 1.3 moles of chromium ions, 0.018 moles of palladium ions and 0.42 moles of aluminum ions are present in one liter of solution are. The carrier is then removed from the solution, dried for 15 hours at a temperature of 120 ° C. and sintered 6 hours at a temperature of 750 ° C. The aluminum oxide

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deposited monolithic catalyst which is thus obtained contains metal oxides in which 0.3 mol of nickel, 1.3 mol Chromium, 0.005 moles palladium and 0.10 moles aluminum are present as metals.

Example 32

An alumina-deposited monolithic carrier prepared in the same manner as in Example 31 was, is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and Immersed aluminum nitrate, with 1.3 moles of nickel ions, 1.3 moles of chromium ions, 0.018 moles of palladium ions and 0.13 moles of aluminum ions are present in one liter of solution. The carrier is then removed from the solution and under the same conditions dried and sintered as in Example 31. The alumina-deposited monolithic carrier thus prepared contains metal oxides, others 0.3 mol nickel, 0.3 mol chromium, 0.005 moles of palladium and 0.03 moles of aluminum are present as metals.

Example 33

A monolithic cordierite support that supports the has a volume dimension of 0.785 liters, is first placed in a commercially available aluminum oxide sol.

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dives. The carrier is then sintered for 3 hours at one Temperature of 700 ° C, whereby garama aluminum oxide is deposited on the carrier. The same operation will repeated three times so that a total of 21 wt. f gamma aluminum oxide is deposited on the cordierite support. The in Alumina-deposited monolithic carrier prepared in this way is dissolved in 3.0 liters of an aqueous solution of one Mixture of nickel nitrate, chromium nitrate, palladium nitrate " Zirconyl nitrate and bismuth nitrate immersed, with 1.1 mol Nickel ions, 1.1 mol chromium ions, 0.018 mol palladium ions, There are 0.073 moles of zirconium ions and 0.073 moles of bismuth ions in 1 liter of solution. The one with nitrates of nickel Chromium, palladium, zirconium and bismuth impregnated carrier is then removed from the solution and dried and sintered under the same conditions as in Example 31. Of the In this way prepared aluminum oxide-deposited monolithic catalyst contains metal oxides in which o, 3 mol Nickel, 0.3 mol of chromium, 0.005 mol of palladium, 0.02 mol of zirconium and 0.02 mol of bismuth are present as metals.

Example 34

An alumina-deposited monolithic carrier of the same type and size as used in Example 33 is placed in 3.0 liters of an aqueous solution of one Mixture of nickel nitrate, chromium nitrate, palladium nitrate, zirconyl nitrate and vanadium trioxide immersed, with 1.1 mol

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Nickel ions, 1.1 mol of chromium ions, 0.018 mol of palladium ions, 0.073 mol of zirconium ions and 0.073 mol of vanadium ions are present in 1 liter of solution. The carrier so impregnated with the nitrates of nickel, chromium, palladium, zirconium and vanadium is then removed from the solution. The support is then dried for 15 hours at a temperature of 120.degree. C. and sintered for 6 hours in a stream of air at a temperature of 750.degree. The resulting alumina-deposited monolithic catalyst contains metal oxides in which 0.3 moles of nickel, 0.3 moles of chromium, 0.005 moles of palladium, 0.02 moles of zirconium and 0.02 moles of vanadium are present as metals.

Example 35

An alumina-deposited monolithic support, also made in the manner used in Example 33 is prepared, is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, Zirconyl nitrate and aluminum nitrate immersed, with 1.1 mol Nickel ions, 1.1 mol chromium ions, 0.018 mol palladium ions, 0.073 mol zirconium ions and 0.18 mol aluminum ions in 1 liter Solution are in place. The carrier is then removed from the solution and under the same conditions as in Example dried and sintered. The alumina-deposited monolithic catalyst obtained in this way

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contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.005 mol of palladium, 0.02 mol of zirconium and 0.05 mol of aluminum are present as metals.

Example 36

An alumina-deposited monolithic support, which is similar to that used in Example 3 3 is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, Chromium nitrate, palladium nitrate, bismuth nitrate and vanadium trioxide immersed, with 1.1 moles of nickel ions, 1.1 moles Chromium ions, 0.018 mol of palladium ions, 0.073 mol of bismuth ions and 0.073 mol of vanadium ions are present in 1 liter of solution. The support thus processed is removed from the solution and dried and sintered under the same conditions as in Example 33. The resulting aluminum oxide deposited

I ₁

dene monolithic catalyst contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.005 mol of palladium, 0.02 mol Bismuth and 0.02 moles of vanadium are present as metals.

Example 37

An alumina-deposited monolithic carrier of the same type and size as used in Example 33 is, in 3.0 liters of an aqueous solution of a mixture

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of nickel nitrate, chromium nitrate, palladium nitrate, bismuth nitrate and aluminum nitrate immersed, with 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.018 moles of palladium ions, 0.073 moles of bismuth ions and 0.18 moles of aluminum ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example 33. The deposited aluminum oxide obtained in this way monolithic catalyst contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.005 mol of palladium, 0.02 moles of bismuth and 0.05 moles of aluminum are present as metals.

Example 38

An alumina-deposited monolithic carrier of the same type and size as that used in Example 33 The carrier is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, vanadium trioxide and aluminum nitrate immersed, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.018 moles of palladium ions, 0.073 moles of vanadium ions and 0.18 moles of aluminum ions in 1 liter Solution are present. Then the carrier is removed from the solution and under the same conditions as in Example dried and sintered. The alumina-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 mol

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22,6377

Chromium, 0.005 moles palladium, 0.02 moles vanadium and 0.05 moles Aluminum are present as metals.

Example 39

An alumina-deposited monolithic support is also used, which in the same Hot as in Example 33 was prepared. The carrier, which has a volume of 0.785 liters, is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and copper nitrate, with 1.1 mol of nickel ions, 1.1 mol Chromium ions, 0.0036 moles of palladium ions and 0.73 moles of copper ions are present in 1 liter of solution. The monolithic support impregnated with the nitrates of nickel, chromium, palladium and copper in this way is then removed from the solution, dried for 18 hours at a temperature of 120 ° C and 5 hours in one Sintered air flow at a temperature of 750 ° C. Of the In this way obtained aluminum oxide-deposited monolithic catalyst contains metal oxides in which o, 3 mol Nickel, 0.3 mol of chromium, 0.001 mol of palladium and 0.2 mol of copper are present as metals.

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22A6377

Example 40

An alumina-deposited monolithic carrier prepared in the same manner as in Example 33 is used again. The carrier is immersed in 3 _r O liters of an aqueous solution of a mixture of Nikkeinitrat, chromium nitrate, palladium nitrate and copper nitrate to give 1.1 mole of nickel ions, 1.1 mol of chromium ions, 0.0073 mole of palladium ions and Q, 36 mole of copper ions in 1 Liters of solution are present. The carrier is then removed from the solution, dried for 18 hours at a temperature of 120.degree. C. and sintered in a stream of air for 5 hours at a temperature of 750.degree. The monolithic catalyst thus obtained contains metal oxides which contain 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium and 0.1 mol of copper as metals.

Example 41

An alumina-deposited monolithic carrier which was prepared in the same manner as in Example 33 is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and copper nitrate, where 1.1 mol of nickel ions, 1.1 mol Chromium ions, 0.011 moles palladium ions and 0.18 moles copper ions

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Are present in 1 liter of solution. The carrier is then made the solution removed and dried and sintered under the same conditions as in Example 40. The one on this Monolithic alumina-deposited monolithic obtained alumina Catalyst contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.003 mol of palladium and 0.05 mol of copper as Metals are present.

Example 42

A monolithic carrier made of ß-spodumene with a volume of 0.765 liters is commercially available available alumina sol immersed and then 3 hours * sintered at a temperature of 700 ° C, so that gamma * aluminum oxide is deposited on the carrier. There · same The process is repeated three times, so that a total of 25% by weight of gamma-aluminum oxide is finally on the β-spodumene support to be deposited. The alumina-deposited monolithic carrier is in 3.0 liters of an aqueous solution of a Mixture of nickel nitrate, chromium nitrate, palladium nitrate and copper nitrate immersed, with 0.64 moles of nickel ions, 1.9 moles Chromium ions, 0.0085 moles of palladium ions and 0.42 moles of copper ions are present in 1 liter of solution. The one with the nitrates of Nickel, chromium, palladium and copper impregnated support is removed from the solution, dried and placed under the same

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Conditions as sintered in Example 40. The one on this Alumina-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.15 mol of nickel / 0.45 moles of chromium, 0.002 moles of palladium and 0.1 moles of copper as Metals are present.

Example 43

An alumina-deposited monolithic Trä- g f which prepares in the same manner as in Example 42, in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate and copper nitrate is immersed, wherein 1.9 mole of nickel ions, 0, 64 moles of chromium ions, 0.0085 moles of palladium ions and 0.42 moles of copper ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example 40. The aluminum oxide-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.45 mol of nickel, 0.15 mol of chromium, 0.002 mol of palladium and 0.1 mol of copper are present as metals »

Example 44

A monolithic cordierite carrier with the 303826/1022

volume of 0.785 liters is immersed in a commercially available aluminum oxide sol. The carrier is then ^{sintered for 3 hours at a temperature of 70O 0} C, so that gamma-aluminum oxide is deposited on the carrier. The same procedure is repeated three times so that a total of 21% by weight of gamma-aluminum oxide is deposited on the support. The thus prepared aluminum oxide-deposited monolithic carrier is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate and zirconyl nitrate, where 1.1 mol nickel ions, 1.1 mol chromium ions, 0.0073 mol palladium ions, 0.36 mol of copper ions and 0.16 mol of zirconium ions are present in 1 liter of solution. The carrier is then removed from the solution, dried for 15 hours at a temperature of 120 ° C. and sintered in a stream of air at a temperature of 750 ° C. for 6 hours. The alumina-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper and 0.05 mol of zirconium are present as metals.

Example 45

An alumina-deposited monolithic carrier is first prepared in the same manner as in Example 44 prepares. The carrier is then immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate,

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Palladium nitrate, copper nitrate and bismuth nitrate, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 moles of palladium ions, 0.36 mol of copper ions and 0.18 mol of bismuth ions are present in 1 liter of solution. The carrier is then made removed from the solution and dried and sintered under the same conditions as in Example 44. The alumina-deposited monolithic support, which in this way is obtained, contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper and 0.05 Moles of bismuth as metals are present.

Example 46

An alumina-deposited monolithic carrier of the same type and size as in Example 44 is in 3.0 liters an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate and vanadium trioxide immersed, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 moles of palladium ions, 0.36 moles of copper ions and 0.18 moles Vanadium ions are present in 1 liter of solution. The carrier is then removed from the solution and under the same conditions dried and sintered as in Example 44. The monolithic alumina-deposited alumina obtained in this way Catalyst contains metal oxides in which 0.3 moles of nickel, 0.3 moles of chromium, 0.1 moles of copper and 0.05 moles of vanadium

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when metals are present

Example 47 ■ "■ ■■ ■ ■. ■. ■■

First, an alumina-deposited monolithic carrier is prepared which is of the same type and Size is like the carrier used in Example 44. Of the

Ί.

Carrier is then in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, Copper nitrate and aluminum nitrate immersed, with 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 moles of palladium ions, 0.36 mol of copper ions and 0.36 mol of aluminum ions are present in 1 liter of solution. The carrier then goes out of solution removed and dried and sintered under the same conditions as in Example 44. The one obtained in this way Alumina-deposited monolithic catalyst contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol Palladium, 0.1 mol of copper and 0.10 mol of aluminum are present as metals.

Example 48

An alumina-deposited monolithic carrier of the same type and size as that in example

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carrier used, is dissolved in 3.0 liters of an aqueous solution immersed in a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate, zirconium nitrate and bismuth nitrate, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 Moles of palladium ions, 0.36 moles of copper ions, 0.073 moles of zirconium ions and 0.073 moles of bismuth ions are present in 1 liter of the solution are. The support is then removed from the solution and dried under the same conditions as in Example 44 and sintered. The alumina-deposited monolithic catalyst obtained in this way contains metal oxides, in which 0.3 moles of nickel, 0.3 moles of chromium, 0.002 moles of palladium, 0.1 moles of copper, 0.02 moles of zirconium and 0.02 moles of bismuth are present as metals.

Example 49

An alumina-deposited monolithic carrier which is the same type and size as that in Example 44 carrier used is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, Copper nitrate, zirconyl nitrate and vanadium trioxide immersed, with 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 mol of palladium ions, 0.36 mol of copper ions, 0.073 mol of zirconium ions and 0.073 mol of vanadium ions are present in 1 liter of solution are. The carrier is then removed from the solution

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and dried and sintered under the same conditions as in Example 44. The alumina-deposited monolithic catalyst obtained in this way contains Metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper, 0.02 mol of zirconium and 0.02 mol Vanadium are present as metals.

Example 50

An alumina-deposited monolithic carrier which is the same type and size as the carrier used in Example 44 is placed in 3.0 liters of an aqueous Solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate, zirconyl nitrate and aluminum nitrate immersed, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 moles of palladium ions, 0.36 moles of copper ions, 0.073 moles Zirconium ions and 0.18 moles of aluminum ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example 44. The alumina-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper, 0.02 mol of zirconium and 0.05 mol of aluminum as metals are present.

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Example 51

An alumina-deposited monolithic carrier, which is the same type and size as the carrier used in Example 44, is immersed in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate, bismuth nitrate and vanadium trioxide, with 1 , 1 mol of nickel ions, 1.1 mol of chromium ions, 0.0073 mol of palladium ions, 0.36 mol of copper ions, 0.073 mol of bismuth ions and 0.073 mol of vanadium ions are present in 1 liter of solution. The carrier is removed from the solution and dried and sintered under the same conditions as in Example 44. The alraainium oxide-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper, 0.02 mol of bismuth and 0.02 mol of vanadium are used as metals are present.

Example 52

An alumina-deposited monolithic support of the type and size of the support used in Example 44 is in 3.0 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate, Bismuth nitrate and aluminum nitrate immersed, with 1.1 mol

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Nickel ions, 1.1 mol of chromium ions, 0.0073 mol of palladium _{ions, O #} 36 mol of copper ions, 0.073 mol of bismuth ions and 0.18 mol of aluminum ions are present in 1 liter of solution. Then, the carrier is removed from the solution and dried and sintered under the same conditions as in Example 44. The aluminum oxide-deposited monolithic catalyst obtained in this way contains metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper, 0.02 mol of bismuth and 0.05 mol of aluminum are used as metals are present.

Example 53

An alumina-deposited monolithic carrier, which is the same type and size as the carrier used in Example 44, is placed in 3.0 liters of an aqueous Solution of a mixture of nickel nitrate, chromium nitrate, palladium nitrate, copper nitrate, vanadium trioxide and aluminum nitrate immersed, where 1.1 moles of nickel ions, 1.1 moles of chromium ions, 0.0073 moles of palladium ions, 0.36 moles of copper ions, 0.073 moles Vanadium ions and 0.18 mol of aluminum ions are present in 1 liter of solution. The carrier is then removed from the solution and dried and sintered under the same conditions as in Example 44. The alumina-deposited monolithic catalyst obtained in this way contains

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Metal oxides in which 0.3 mol of nickel, 0.3 mol of chromium, 0.002 mol of palladium, 0.1 mol of copper, 0.02 mol of vanadium and 0.05 mol of aluminum are present as metals.

Four different samples are prepared as representative examples of prior art catalysts for the purpose of comparison with the catalysts, which according to the invention as described in the examples above.

Sample 1

1 liter of a granular carrier, which is made of

commercially available activated chi-alumina from et-

wa 6 to 8 meshes per 6.45 cm consists, becomes 1.50 liters of an aqueous solution of a mixture of nickel nitrate and Chromium nitrate added, where I? 5 moles of nickel ions and 1.5 Moles of chromium ions are present in 1 liter of solution. The carrier thus impregnated with the nitrates of nickel and chromium becomes removed from solution, 15 hours at a temperature of Dried at 120 ° C and sintered for 3 hours in a stream of air at a temperature of 750 ° C. The resulting catalyst contains metal oxides in which 0.75 mol of nickel and 0.75 mol of chromium are present as metals in 1 liter of catalyst.

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Sample 2 '''""^; · '

A liter of a granular carrier, which consists of commercially available activated gamraa aluminum oxide of about 6 bit 8 nibs per 6.45 cm ² , is added to 1.35 liters of an aqueous solution of a mixture of chromium nitrate and copper nitrate, with 2.2 moles of chromium ions and 1.1 moles of copper ions are present in 1 liter of solution. The carrier impregnated in this way with the nitrates of chromium and copper is removed from the solution and dried and sintered under the same conditions as those used to produce sample 1. The catalyst obtained in this way contains metal oxides in which 1.0 mol of chromium and 0.5 mol of copper are present as metals in 1 liter of catalyst.

Sample 3

1 liter of an extrusion-molded support, which was obtained from commercially available granulated activated delta-aluminum oxide of about 6 to 8 mesh in 6.45 cm ² , is immersed in 1.20 liters of an aqueous solution of a mixture of nickel nitrate, chromium nitrate and copper nitrate, where I »3 moles of nickel ions, 2.3 moles of chromium ions and 1.3 moles of copper ions are present in 1 liter of solution. The carrier impregnated in this way with the nitrates of nickel, chromium and copper is removed from the solution and under the same conditions

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dried and sintered as they are used to prepare sample 1 were applied. The catalyst obtained in this way contains metal oxides in which 0.5 mol of nickel and 1.0 mol of chromium and 0.5 moles of copper are present as metals in 1 liter of catalyst.

Sample 4

1 liter of a carrier of the same type as for sample 1, is added to 1.50 liters of an aqueous solution of a mixture of manganese nitrate, chromium nitrate and copper nitrate, where 1.0 mole of manganese ions, 2.0 mole of chromium ions and 1.0 mole of copper ions are present in 1 liter of solution. Of the Carrier is then removed from the solution and taken under the same Dry and sintered conditions as used to prepare Sample 1. That way obtained catalyst contains metal oxides, in which 0.5 mol of manganese, 1.0 mol of chromium and 0.5 mol of copper as metals in 1 Li-. ter catalyst are included.

Tests are carried out with samples 1 to 4 and the catalysts prepared in examples 1 to 53, to determine the efficiencies of these catalysts; Gases A and B, which have the compositions given in Table I. are used as models in the tests, with the model gas A for oxidation reactions and that

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Model gas B applies for reduction reactions. The oxidation and reduction reactions are carried out at a space velocity of 15,000 hours. The temperature of the catalyst bed is varied in the range from 100 to 600.degree. C. so that a general relationship between temperature and conversion efficiency of carbon monoxide, propane and / or nitrogen monoxide is determined. "Conversion efficiency" as mentioned here is intended to mean a percentage of carbon monoxide, propane or nitric oxide, which is in non-toxic compounds such as Carbon dioxide, nitrogen and water is converted.

Table I. Model gas B Components Model gas A 2.0 Carbon monoxide, full 2.0 500 Propane, TIe. per million 500 1000 Nitric oxide, TIe. per million 1000 12.0 Carbon dioxide, vol.% 12.0 0 Oxygen, vol.% 2.5 rest nitrogen rest

The relationship between the conversion efficiency and the temperature thus determined is indicated by the graph which is illustrated in the accompanying drawing will.

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The temperature at which the conversion efficiencies of carbon monoxide, propane and / or nitrogen monoxide Reaching 90% results from the relationship shown by this curve. These temperatures are used for comparison in particular with regard to the effectiveness between the catalysts used in the above Examples 1 to 53 described and samples 1 to 4 were prepared. It can be seen in this case that the lower the temperature, the higher the low temperature activity of the catalyst, which provides the conversion efficiency of 90% and vice versa. The goals of the Invention are therefore all the better achieved by catalysts which have the 90% conversion efficiency at the lower Show temperatures.

. Tests are also carried out to evaluate the durability of the catalysts used in the examples 1 to 53 and samples 1 to 4 were prepared. For this purpose, the catalysts to be tested are in a front muffler of an exhaust system of a four-stroke four-cylinder Combustion engine with a displacement of 1600 cm. The machine dynamometer used is one of the kind that is widely used. The engine runs on unleaded gasoline and cyclically driven through the operating modes including

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Acceleration, normal cruising speed «deceleration and idling or stopping under the conditions analogous to the durability test standard of the AMA (Automobile Manufactures' Association, United States of America). Will be accompanying air into the exhaust system upstream of the catalytic converter

Il

leads where the catalyst is used as an oxidation catalyst, while in the test where the catalyst is used is used as a reduction catalyst, bypass air is not supplied to the exhaust system.

The catalysts that worked on the tests in which the engine was driven to simulate a 5000 km drive of the motor vehicle, are tested for effectiveness using model gases A and B, whereby the temperatures are determined which are 90% Create conversion efficiency of the catalysts. The temperature difference that the 90% conversion through the Catalysts obtained before and after the durability tests considered to provide a useful criterion for evaluating the durability of the catalyst · per the smaller such a difference is, the higher the durability of the catalyst will be. The results of the above tests mentioned are demonstrated in Table II.

Review of Table II clearly reveals that the 3098 2 6/1022

Catalysts of Examples 1 to 53 are far superior to the catalysts of the prior art such as Samples 1 to 4 in terms of low-temperature effectiveness and durability.

Tabel : nan treenail ^C 3 8 NO ♦♦ 90% Conversion, c SV NO · ♦ EGG catalyst 360 36O iacn * Continuous- 400 415 Temperature at CO * -3 ^ 5 350 ability test 390 410 . Catalysts rest: 290 . 360 36O CO * 390 4io 290 350 355 320 390 400 Example l 290 365 3 ^ 5 320 405 "395 "2 290 355 340 315 400 400 Il 3 305 365 3 ^ 0 315 400 400 Il k 300 380 370 325 420 410 " ⁵ 305 355 360 325 395 415 »6 310 390 370 320 43a 420 • ι 7 310 390 380 3'to 430 44o • ι β 320 360 360 3 / tO 4oo 410 ι 9 320 350 3 40 345 390 400 ¹¹ IO 305 360 350 345 390 4oo '»11 300 360 3.45. 335 4oo 410 ". 12 305 355 345 325 390 405 Ii I ₃ 320 360 345 330 385 380 H xk 300 360 350 350 385 38O • ι I ₅ 310 360 350 330 370 38O "16 305 360 355 315 380 385 ^11th ' 17th 305 355 360 32Ό 370 390 »18th 305 360 360 310 375 395 ι · I ₉ 300 360 355 310 38O 390 ¹¹ 20 300 3tÖ * $> 310 385 390 • ι 21 305 310 • ι 22 315 • ι 23 315 309826/102 »! 24

Table II (continued)

Temperature at mitrriscrem ^C ₃ V NO ·· 901 Conversion. C. ülller'hartia- C ₃ H ₀ NO ·· Teät catalyst 365 350 rtäcfH ability test 385 385 Catalysts CO * 365 350 CO 390 395 310 370 355 320 390 395 Example 25 310 360 345 320 390 390 ¹¹ 26 310 365 380 320 380 390 "'27 310 360 380 320 375 390 "28 305 370 380 310 38O ^ 390 "29 300 370 375 310 385 395 ¹¹ 30 315 360 355 320 300 385 μ ₃₁ 315 365 350 320 380 380 "32 310 365 360 320 375 380 "33 3X0 370 380 320 39p 400 • ι 34 315 370 38O 320 395 400 ¹¹ 35 315 375 370 325 395 395 "36 315 355 350 325 395 420 ι · 37 315 360 355 325 400 410 ¹¹ . 38 285 360 350 320 405 410 • ι ₃₉ 280 360 350 315 405 405 "4o 290 360 350 320 400 4io H 4i 295 360 350 310 380 385 »42 295 365 360 315 385 390 «43 285 365 360 2 ^ 5 390 390 «44 290 365 355 305 38O 385 • ι 45 290 360 360 305 375 385 Example 46 290 365 360 300 380 390 μ 47 290 365 365 300 375 380 ι · · 48 290 370 36O 300 385 390 • ι 4 ₉ 295 370 36Ö 300 385 ₍ 390 "50 290 360 360 305 375 385 ₅₁ 295 395 405 305 500 510 "52 295 425 420 300 510 500 "53 4oo 405 395 480 490 490, Sample 1 330 400 410 415 480 495 • ι 2 335 405 "3 330 400 H 4

«? K / 1 ü 2 2

Comment! The characters ■ show "*" or "**"

Tests using model gases A and B respectively.

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Claims (19)

received nm 15. m _. &, · vuv, 22a6377 patent claims'. ■. ·. ■. ■. ■■ ■■ 1. Catalyst, consisting of or containing a support and oxides of nickel, chromium and palladium. 2. Catalyst according to claim 1, characterized in that that it contains the oxides of nickel and chromium in a total amount of 0.1 to 3.5 moles of nickel and chromium, and the oxide of Contains palladium in an amount of more than 0.0003 moles of palladium per liter of the support. 3. Catalyst according to claim 2, characterized in that the palladium in a concentration of 0.0003 to 0.01 mol per liter of the carrier is included. 4. Catalyst according to claim 2, characterized in that the nickel and chromium oxides in the molar ratio of 1: 6 to 6: 1 are available. 5. A catalyst according to claim 2, characterized in that it further comprises at least one of the oxides of zirconium, bismuth, vanadium and aluminum. 6. Catalyst according to claim 5, characterized in that that the molar concentration of the metal components or metal components these oxides, of which 309826/1022 at least one is present, ranging from 1/25 to 1/4 of the total concentration of the metal components of the nickel and Chromium oxide lies in the presence of aluminum oxide. 7. Catalyst according to claim 5, characterized in that that the molar concentration of the metal component or metal components of these oxides, of which at least one is present, in the range from 1/50 to 1/5 of the total concentration of the metal components of the nickel and chromium oxides in Absence of aluminum oxide. 8th,. Catalyst according to claim 2, characterized in that that it also has copper oxide. 9. Catalyst according to claim 8, characterized in that the molar concentration of the metal component of the Copper oxide is in the range from 1/20 to 1/3 of the total concentration of the metal components of the nickel and chromium oxides. 10. Catalyst according to claim 1, characterized in that the carrier is a monolithic carrier. 11. Catalyst according to claim 10, characterized in that the support consists of at least one of the materials cordierite, ß-spodumene and alpha-aluminum oxide are formed is. 309826/1022 12. Catalyst according to claim 11, characterized in that the carrier further comprises an activated aluminum oxide which is deposited on the carrier material is. 13. Catalyst according to claim 12, characterized in that the activated aluminum oxide is gamma-aluminum oxide or kappa-aluminum oxide. 14. Catalyst according to claim 1, characterized in that the carrier is a non-monolithic carrier. 15. Catalyst according to claim 14, characterized in that the carrier is formed from at least one of the materials alpha-aluminum oxide, gamma-aluminum oxide, delta-aluminum oxide and chi-aluminum oxide. 16. Catalyst according to claim 1, characterized by a support; Nickel and chromium oxides, which contain a total of 0.1 to 3.5 moles of nickel and chromium, the present in a molar ratio of It6 to 6t1 per 1 liter of this support> 0.0003 to 0.01 mol of palladium per 1 liter of the support; and at least one of the oxides of zirconium, bismuth, vanadium and aluminum in a molar concentration of 1/25 to 1/4 of the total concentration of nickel and chromium in the presence of aluminum oxide. T) O ^ f § Xh / A 0 2 X 17. Catalyst according to claim 1, characterized by a support; Nickel and chromium oxides with a content a total of 0.1 to 3.5 moles of nickel and chromium, which in a molar ratio of 1: 6 to 6: 1 per 1 liter of the carrier exist? 0.0003 to 0.01 moles of palladium per 1 liter of the support; and at least one of the oxides of zirconium, bismuth and vanadium in a molar concentration of 1/50 to 1/5 of the total concentration of nickel and chromium. 18. Catalyst according to claim i, characterized by a carrier; Nickel and chromium oxides, which contain a total of 0.1 to 3.5 moles of nickel and chromium, in a molar ratio from 1: 6 to 6: 1 per liter of carrier; 0.0003 to 0.01 moles of palladium per 1 liter of the support; at least one of the oxides of zirconium, bismuth, vanadium and aluminum in a molar concentration of the metal component from 1:25 to 1: 4 of the total concentration, nickel and chromium in the presence of aluminum oxide; and a copper oxide in one molar concentration of the metal component from 1/20 to 1/3 of the total concentration of the nickel and chromium oxides. 19. Catalyst according to claim!, Gekexroseldinefc tocheteem carrier? Nickel and chromium oxides with a total content of 0 ^ 1 to 3.5 moles of nickel and chromium, which are present in a molar concentration of 1: 6 to 6: 1 per 1 liter of the carrier? 0.0003 309826Π022 to O, Ol moles of palladium in 1 liter of the carrier? at least one of the oxides of zirconium, bismuth and vanadium in a molar concentration of the metal component of 1/50 to 1/5 of the total concentration of nickel and chromium; and a copper oxide in
a molar concentration of the metal component of 1/20 to 1/3 of the total concentration of the metal components of the nickel and chromium oxides. 309826/1022