DE102014224470A1 - Removal of oxygen from hydrocarbon gases - Google Patents

Abstract

The present invention is the use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons, characterized in that one or more catalysts as active components a) one or more alkali metals, b) one or more metals selected from the group comprising gold and cadmium and c) one or more metals selected from the group comprising palladium, platinum, rhodium, iridium and ruthenium, wherein the active components a), b) and c) independently of one another in metallic form, as an alloy or in the form of Salts are present.

Description

The invention relates to the use of catalysts for the removal of oxygen from gases containing ethylenically unsaturated hydrocarbons (hydrocarbon gases).

Ethylenically unsaturated hydrocarbons, such as ethylene or propylene, are standard commodities of the chemical industry. Corresponding gases naturally have only a limited degree of purity and may contain, for example, oxygen as an impurity, which is a hindrance to the further use of the hydrocarbon gases and should be removed from the hydrocarbon gases. This can be done, for example, by oxidative purification in which oxygen is reacted with hydrocarbons of the hydrocarbon gas to form non-hindering or easily separable products such as carbon dioxide (CO ₂ ) and water.

The oxidative cleaning is widely used to clean exhaust gases with low content of volatile or easily vaporizable organic substances, also called VOC (Volatile Organic Compounds). For this purpose, the VOCs are often converted by means of catalytic oxidation to CO ₂ and water. Common catalyst systems contain as catalytically active species noble metals, such as palladium or platinum, which are supported, for example on oxidic supports such as Al ₂ O ₃ , SiO ₂ , zeolite, TiO ₂ or ZrO ₂ . Such oxidation catalysts usually show a "light-off" behavior, ie only from a specific temperature, the so-called "light-off" temperature, the catalysts are active. Turnover curves jump around the "light-off" temperature, and in a relatively narrow temperature range, sales increase from 0% to 100%.

So describes Van de Beld in Chemical Engineering and Processing 34, (1995), pages 469-478 the total oxidation of ethene and propane on Pd catalysts supported on Al ₂ O ₃ . Here, the ethene conversion at 260 ° C is only 20% and only from temperatures above 400 ° C ethene is fully implemented. Also Rusu discusses in Environmental Engineering and Management Journal, 2003, Vol. 2, no. 4, pages 273 to 302 the oxidation of ethene. The most commonly used catalyst systems are Pd or Pt on TiO ₂ , Al ₂ O ₃ or SiO ₂ . Pt is recommended as the most suitable catalyst. Hosseini recommends in Catalysis Today, 122, (2007), pages 391-396 for the total oxidation of propene Pd and Au on TiO ₂ as catalyst. The light-off temperature is 200 ° C and no CO formation occurs. For the CO oxidation is taught by Venezia in Applied Catalysis A, 251, (2003), pages 359-368 Au-Pd catalysts on SiO ₂ . From temperatures of> 160 ° C CO can be completely converted. From the EP 2656904 are known catalysts for the purification of exhaust gases from diesel engines. The catalysts contain a catalytic coating with Pt, Pd and a carbon-storing compound, such as zeolite, as well as another coating with Pd and Au.

So often described is the use of catalysts for the oxidative purification of gas mixtures containing small amounts of hydrocarbons, as is typical for industrial or car exhaust. The oxidative purification is particularly problematic if the gases to be purified consist essentially of hydrocarbons, especially if the gases additionally contain considerable amounts of oxygen. Because the current catalysts require relatively high temperatures to achieve their catalytic activity or their "light-off" temperature for the oxidation reactions. Especially at higher temperatures, however, it may lead to the formation of unwanted by-products or even decomposition or uncontrolled polymerization of hydrocarbons. At lower temperatures, however, the oxygen is not sufficiently converted in the previously known methods and no adequate cleaning effect is achieved.

Against this background, the task was to provide measures that allow sufficient removal of oxygen from ethylenically unsaturated hydrocarbons containing gases at the lowest possible temperatures, especially at temperatures of <200 ° C, with the formation of by-products, such as carbon monoxide, minimized if possible should be.

• a) ein oder mehrere Alkalimetalle,
• b) ein oder mehrere Metalle ausgewählt aus der Gruppe umfassend Gold und Cadmium und
• c) ein oder mehrere Metalle ausgewählt aus der Gruppe umfassend Palladium, Platin, Rhodium, Iridium und Ruthenium enthalten, wobei die Aktivkomponenten a), b) und c) unabhängig voneinander in metallischer Form, als Legierung oder in Form von Salzen vorliegen.

The present invention is the use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons, characterized in that one or more catalysts as active components

• a) one or more alkali metals,
• b) one or more metals selected from the group comprising gold and cadmium and
• c) one or more metals selected from the group comprising palladium, platinum, rhodium, iridium and ruthenium, wherein the active components a), b) and c) are present independently of one another in metallic form, as an alloy or in the form of salts.

Gases containing one or more ethylenically unsaturated hydrocarbons are also referred to below as hydrocarbon gases.

The ethylenically unsaturated hydrocarbons preferably contain 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. Examples of ethylenically unsaturated hydrocarbons are ethylene, propylene, butadiene, butene, hexene, cyclohexene or aromatic hydrocarbons, such as benzene, toluene or styrene. The ethylenically unsaturated hydrocarbons may optionally bear functional groups, such as halides. Examples of these are vinyl halides or allyl halides, such as vinyl chloride or allyl chloride. Preferred ethylenically unsaturated hydrocarbons are ethylene, propylene, butene, pentene, hexene or cyclohexene. Particularly preferred are ethylene, propylene or butene. Most preferred is ethylene. The gases may also contain mixtures of several ethylenically unsaturated hydrocarbons.

The hydrocarbon gases preferably contain from 70 to 99.9% by volume, more preferably from 90 to 99.9% by volume, more preferably from 95 to 99.5% by volume, and most preferably from 97 to 99% by volume of ethylenic unsaturated hydrocarbons.

The hydrocarbon gases preferably contain from 0.1 to 30% by volume, more preferably from 0.1 to 5% by volume, and most preferably from 1 to 3% by volume of oxygen.

The hydrocarbon gases may optionally contain one or more further impurities, for example selected from the group comprising nitrogen, carbon dioxide, carbon monoxide and other organic components other than the ethylenically unsaturated hydrocarbons, such as saturated, optionally functionalized hydrocarbons. Such saturated hydrocarbons preferably contain 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Examples of saturated, optionally functionalized hydrocarbon gases are methane, ethane, propane, butane, pentane or especially acetic acid. The further impurities in the hydrocarbon gases are for example from 0 to 20% by volume, preferably from 0 to 5% by volume, more preferably from 0.01 to 5% by volume and most preferably from 0.1 to 2% by volume .-% contain.

The above data in% by volume relate in each case to the total volume of the respective hydrocarbon gas. Overall, the components of a hydrocarbon gas add up to 100 vol .-%.

The composition of the hydrocarbon gases and the other conditions, such as pressure and temperature, are generally chosen so that the ignition limit is preferably in accordance with DIN EN 1839-13 is fallen below. The application of the stipulations of DIN EN 1839-13 is familiar to the skilled person.

The catalytically active species of the catalysts are based essentially on the active components a), b) and c).

As active component a) are preferably lithium, sodium, potassium, rubidium, cesium; most preferably potassium and cesium, and most preferably potassium. As active component b) gold is preferred. Preferred active component c) is palladium.

The weight ratio of the active component b) to the active component c) is preferably 1:10 to 10: 1, more preferably 1: 4 to 4: 1, and most preferably 1: 2 to 2: 1. The weight ratio of active component a) to active component c) is preferably 1:10 to 10: 1, more preferably 1: 4 to 4: 1, and most preferably 1: 2 to 2: 1.

The catalysts preferably contain 0.1 to 15.0 wt%, more preferably 0.5 to 10 wt%, even more preferably 1 to 8 wt%, and most preferably 2 to 6 wt% of the active component a). The catalysts preferably contain 0.1 to 10.0 wt .-%, particularly preferably 0.5 to 7 wt .-%, most preferably 1 to 5 wt .-% of active component b). The catalysts preferably contain 0.1 to 10.0 wt .-%, more preferably 0.5 to 7 wt .-%, most preferably 1 to 5 wt .-% of active component c). The data in% by weight are based on the total weight of the catalyst.

To prepare the catalysts, the active components a), b) and c) are preferably used in the form of their salts, for example in the form of their acetates, halides, oxides, hydroxides or nitrates. The active components a) are particularly preferably used in the form of their acetates.

In addition to the active components a), b) and c), the catalysts may additionally contain one or more carriers. The active components can be applied to carriers or fixed or supported on the carriers.

Examples of carriers are oxides or mixed oxides of metals or semimetals, such as silicon, tin, aluminum, iron, zirconium, titanium, cerium, lanthanum or magnesium. Examples of mixed oxides are aluminosilicates, magnesium silicate, magnesium aluminum silicates or zeolites. Suitable supports are also carbon, carbides or nitrides, for example silicon carbides, boron carbides or boron nitrides. preferred Carriers are SiO ₂ , Al ₂ O ₃ , La ₂ O ₃ , ZrO ₂ , MgO, Fe ₂ O ₃ , SnO ₂ or TiO ₂ . Particularly preferred supports are SiO ₂ or Al ₂ O ₃ . The most preferred carrier is fumed SiO ₂ .

The catalysts may be supported or unsupported. Preferred are supported catalysts. Examples of supported catalysts are shelled or impregnated catalysts.

Furthermore, the catalysts may contain one or more dopants, for example inorganic salts, such as halides, oxides, nitrates, nitrites, silicates, carbonates, borates, aluminates, molybdates, tungstates, vanadates, niobates, tantalates, titanates, zirconates or in general polyoxometalates, if appropriate with alkaline earth metal cations, in particular alkali metal cations as counterions. Examples of polyoxometalates are polymolybdates, polyvanadates or polytungstates.

The catalysts have BET surface areas of preferably 30 to 500 m ² / g, particularly preferably from 150 to 450 m ² / g and most preferably from 170 to 350 m ² / g (determination according to DIN 66131 with nitrogen).

The catalysts may be in the usual geometries, such as in the form of rings, pellets, cylinders, spheres or monoliths.

The preparation of the catalysts can be carried out in a known per se, such as in the DE 10 2006 058 800 A1 . EP 565952 . DE 10 2012 003 236 A1 . WO 2005/065819 A1 or WO 2010 / 056275A1 described.

For example, the catalysts can be prepared by applying one or more active components and optionally one or more dopants to carriers. It is also possible to apply one or more precursor compounds of the active components and optionally one or more dopants to carriers. The precursor compounds of the active components can be converted into active components in a further step.

The application is preferably carried out by means of impregnation, spraying, vapor deposition, dipping or precipitation of appropriate solutions, in particular aqueous solutions.

Examples of precursor compounds are salts of the active components, such as their acetates, halides, nitrates, oxides or hydroxides. The conversion of precursor compounds into active components can be carried out in a conventional manner, for example by reducing, for example with hydrazine hydrate, formaldehyde, hydrogen, ethene, propene, butene or forming gas as reducing agent. The activation can also be carried out under reaction conditions in the reactor, preferably by reducing with ethene, propene, butene or hydrogen-containing gas mixtures. If appropriate, the catalyst thus obtained can be adjusted to the desired residual moisture content by means of drying. If active components are applied as the halides, the halide content may, after application and fixation or reduction of the active components can be reduced, for example by washing with water or aqueous neutral or alkaline solutions, for example, NH _3, N ₂ H _4, (NH _{4) 2} CO ₃ , KOH, NaOH, KHCO ₃ , K ₂ CO ₃ , NaHCO ₃ , Na ₂ CO ₃ , Mg (OAc) ₂ , NaOAc, KOAc. Preference is given here to water. The halide content is preferably ≦ 2000 ppm, more preferably ≦ 1000 ppm, and most preferably ≦ 500 ppm.

Preferably, one or more active components b) and one or more active components c) and optionally one or more dopants and then one or more active components a) or one or more precursor compounds of the active components a) are first applied to the carrier. It is also preferable to first apply one or more precursor compounds of the active components b) and one or more precursor compounds of the active components c) and optionally one or more dopants to carriers and then convert them into active components, for example by reducing, and then one or more active components a) or one or more precursor compounds of the active components a) applied to the carrier.

The removal of oxygen from hydrocarbon gases can be carried out in conventional reactors in a conventional manner. Preferred reactors are tubular reactors, tube-bundle reactors or tray reactors. The reactors are charged with one or more catalysts according to the invention. The reactor is flowed through by the hydrocarbon gas to be purified. The hydrocarbon gas to be purified can be passed through the reactor several times, preferably only once. In the reactor there is a pressure of preferably 1 to 20 bar and more preferably 5 to 15 bar.

The hydrocarbon gas has a temperature of preferably ≦ 200 ° C., more preferably ≦ 180 ° C. and most preferably ≦ 160 ° C., when entering or entering the reactor.

The gas mixture leaving the reactor has a temperature of preferably ≦ 200 ° C., more preferably ≦ 190 ° C., and most preferably ≦ 180 ° C.

The temperature of the gas mixture leaving the reactor differs from the temperature of the gas mixture entering the reactor by preferably ≦ 50 ° C., more preferably ≦ 30 ° C., more preferably ≦ 25 ° C., even more preferably ≦ 20 ° C. and most preferably ≤ 15 ° C.

The temperature of the reactor temperature control is preferably ≦ 200 ° C., more preferably ≦ 190 ° C., and most preferably ≦ 180 ° C., and preferably ≥ 150 ° C. The reactor temperature is the temperature of the medium with which the reactor is heated.

The reactor can be operated adiabatically, isothermally or preferably polytropically. This can lead to hot spots locally within the reactor. Hot spots are local temperature maxima. In isothermally operated reactors, the temperature of the gas mixture leaving the reactor preferably corresponds to the temperature of the reactor temperature control. In the case of adiabatic or polytropic operation, the temperature of the gas mixture leaving the reactor is preferably higher than the temperature of the reactor temperature control.

The degree of conversion of oxygen is preferably 50 to 99.9%, more preferably 90 to 99.9%, even more preferably 95 to 99.9% and most preferably 96 to 99.9%. The degree of conversion denotes the molar ratio of the oxygen which has been removed from the hydrocarbon gas in the course of the oxidative purification according to the invention, and the oxygen of the hydrocarbon gas which has been subjected to the inventive oxidative purification.

After carrying out the removal of oxygen according to the invention, the hydrocarbon gases preferably contain ≦ 10% by volume, more preferably ≦ 3% by volume and most preferably ≦ 0.01% by volume of oxygen, based in each case on the volume of the total gas stream of the purified hydrocarbon gas , In the course of the procedure according to the invention, the hydrocarbon gases are thus completely or partially freed of oxygen.

In an alternative approach, additional hydrogen may be introduced into the reactor or mixed with the hydrocarbon gas to be purified prior to entering the reactor. The amount of hydrogen generally depends on how much oxygen is contained in the hydrocarbon gas and should be reacted with hydrogen to form water.

Preferably, no further gas or agent is introduced into the reactor with the hydrocarbon gas to be purified. For clarity, it should be noted that in particular no oxygen is added to the hydrocarbon gas. During the execution of the cleaning process, therefore, preferably only the hydrocarbon gas to be purified is introduced into the reactor.

With the process according to the invention, oxygen-containing hydrocarbon gases can be freed from oxygen by oxidation of ethylenically unsaturated hydrocarbons. Oxygen is generally converted into carbon dioxide and water. Portions of the ethylenically unsaturated hydrocarbons of the hydrocarbon gases are generally converted to carbon dioxide. Surprisingly, significantly lower "light-off" temperatures for the oxidative purification of hydrocarbon gases could be achieved with the catalysts of the invention and the process, for example, even at temperatures well below 200 ° C are performed. Common platinum or palladium-oxidation catalysts showed in this application, even at temperatures up to 245 ° C, only low oxygen conversions, while with catalysts of the invention, for example, at 150 ° C, oxygen conversions of> 90% are possible. In addition, the formation of undesired by-products can be suppressed or even completely ruled out. By-products are, for example, carbon monoxide and other partial oxidation products, such as aldehydes, esters or other hydrocarbons. The oxygen contained in the hydrocarbon gas can be completely or almost completely converted to carbon dioxide and water.

The following examples serve to further illustrate the invention:

General procedure:

Removal of oxygen from a hydrocarbon gas:

The catalyst given in the respective comparative example or example was charged with a gas mixture consisting of 98% by volume of an ethylenically unsaturated hydrocarbon and 2% by volume of oxygen in a tube reactor heated with oil (length: 2000 mm, inner diameter: 19 mm). The catalyst volume in the tubular reactor was 217 cm ³ . The temperatures given in the examples refer, unless expressly stated otherwise, to the oil feed temperature of the reactor temperature. The reaction pressure in all examples was 9 bar.

Definition of abbreviations:

• - GHSV (gas hourly space velocity): quotient of the volume flow (m ³ / h) of the hydrocarbon gas and the reactor volume [m ³ ].
• Selectivity: Ratio of the number of moles of oxygen converted to the respective product and the number of moles of the total oxygen reacted in the reactor.
• - Forming gas: Gas mixture consisting of 5% by volume of hydrogen and 95% by volume of nitrogen.

Comparative Example 1

Pt catalyst on Al ₂ O _{3 support} :

Preparation of the catalyst:

To 95 g of Al ₂ O _{3 support} , a tetraammineplatinum (II) hydroxide solution (10 wt.% Pt) was added and then rotated on a rotary evaporator for 2 h at 10 rpm. Thereafter, solvent was evaporated in vacuo to give an intermediate having a residual moisture content of 8.7% by weight based on the total weight of the intermediate.

Then was formed for 16 h at 600 ° C with the forming gas and then calcined in an oven at 600 ° C for 16 h under air atmosphere.

The catalyst thus obtained had a platinum content of 1.05 wt .-%.

The catalyst was tested according to the above-mentioned general procedure:
The ethylenically unsaturated hydrocarbon used was ethene. At 240 ° C and a GHSV of 3900 1 / h 40% of the originally present in the hydrocarbon gas O _{2 were} implemented. In addition to CO ₂ and water, the by-products CO were formed with a selectivity of 1% and acetaldehyde with a selectivity of <1%.

Comparative Example 2:

Palladium / gold catalyst on SiO _{2 support} :

Preparation of the catalyst:

An aqueous mixture containing 5.84 g of H [AuCl ₄ ] and 7.96 g of H ₂ [PdCl ₄ ] in 80 ml of deionized water was applied to 100 g of SiO _{2 support} in a rotary evaporator at <100 mbar. In the sequence was dried at 80 ° C at <30 mbar. Thereafter, the precious metals were washed with saturated NaHCO ₃ solution like. It was again dried at 80 ° C in vacuo (<30 mbar). The precipitation step was repeated again. Thereafter, the catalyst was washed continuously with demineralized water (conductivity <10 μS) until no precipitate of AgCl (turbidity of the solution) could be detected in the wash water by precipitation reaction with silver nitrate solution. Subsequently, the catalyst was dried with hot air (80 ° C). To fix the noble metals, the catalyst was formed for 7 h at 200 ° C with the forming gas.

The catalyst was tested according to the above-mentioned general procedure:
The ethylenically unsaturated hydrocarbon used was ethene. At an oil bath temperature of 200 ° C and a GHSV of 3000 1 / h 94% of the originally present in the hydrocarbon gas O _{2 were} implemented at a temperature of 220 ° C, an O ₂ conversion of 97% was achieved. Apart from CO ₂ and water, no other products were produced.

Example 3:

Palladium / gold catalyst with 2.5 wt .-% potassium as potassium acetate on SiO _{2 support} , based on the total weight of the catalyst:

Preparation of the catalyst:

On 100 g of palladium / gold catalyst on SiO _{2 support} from Comparative Example 2, a solution of 6.44 g of potassium acetate in 90 ml of water was applied in a rotary evaporator with rotation. Finally, the thus impregnated catalyst was dried in a hot air stream at 80 ° C.

The catalyst was tested according to the above-mentioned general procedure:
The ethylenically unsaturated hydrocarbon used was ethene. At a temperature of 170 ° C and a GHSV of 3000 1 / h 97% of the originally present in the hydrocarbon gas O _{2 were} implemented. Apart from CO ₂ and water, no other products were produced.

Example 4:

Palladium / gold catalyst with 3.5 wt .-% potassium acetate on SiO _{2 support} , based on the total weight of the catalyst:
The preparation of the catalyst was carried out analogously to Example 3, with the only difference that a solution of 9 g of potassium acetate in 90 ml of water was used.

The catalyst was tested according to the above-mentioned general procedure:
The ethylenically unsaturated hydrocarbon used was ethene. At a temperature of 150 ° C and a GHSV of 3000 1 / h 97% of the originally present in the hydrocarbon gas O _{2 were} implemented. Apart from CO ₂ and water, no other products were produced.

Example 5:

Palladium / gold catalyst with 2.5 wt .-% potassium acetate on SiO _{2 support} , based on the total weight of the catalyst:
The preparation of the catalyst was carried out analogously to Example 3. The catalyst was tested according to the abovementioned general procedure:
Propene was used as the ethylenically unsaturated hydrocarbon. At a temperature of 170 ° C and a GHSV of 2300 1 / h 93% of the originally present in the hydrocarbon gas O _{2 were} implemented. Apart from CO ₂ and water, no other products were produced.

Comparative Example 6:

Platinum catalyst with 0.1 wt .-% platinum based on the total weight of the catalyst on alumina balls (based on ABCR).

The catalyst was tested according to the above-mentioned general procedure:
Propene was used as the ethylenically unsaturated hydrocarbon. At 230 ° C temperature and a GHSV of 2300 1 / h 13% of the originally present in the hydrocarbon gas O _{2 were} implemented. In addition to CO ₂ and water, the by-product CO was formed with a selectivity of 4%.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 2656904 [0004]
• DE 102006058800 A1 [0026]
• EP 565952 [0026]
• DE 102012003236 A1 [0026]
• WO 2005/065819 A1 [0026]
• WO 2010/056275 A1 [0026]

Cited non-patent literature

• van de Beld in Chemical Engineering and Processing 34, (1995), pages 469 to 478 [0004]
• Rusu discusses in Environmental Engineering and Management Journal, 2003, Vol. 2, no. 4, pages 273 to 302 [0004]
• Hosseini recommends in Catalysis Today, 122, (2007), pages 391-396 [0004]
• CO oxidation teaches Venezia in Applied Catalysis A, 251, (2003), pages 359-368 [0004]
• DIN EN 1839-13 [0014]
• DIN EN 1839-13 [0014]
• DIN 66131 [0024]

Claims (10)

Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons, characterized in that one or more catalysts as active components a) one or more alkali metals, b) one or more metals selected from the group comprising gold and cadmium and c ) one or more metals selected from the group comprising palladium, platinum, rhodium, iridium and ruthenium, wherein the active components a), b) and c) are present independently of one another in metallic form, as an alloy or in the form of salts. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claim 1, characterized in that as active component a) potassium or cesium is used. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claim 1 or 2, characterized in that as active component c) palladium is used. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claim 1 to 3, characterized in that one or more catalysts contain 0.1 to 15.0 wt .-% of active component a), based on the Total weight of the catalyst. Use of catalysts for removing oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claims 1 to 4, characterized in that one or more catalysts contain 0.1 to 10.0 wt .-% of active component b), based on the total weight of the catalyst. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claim 1 to 5, characterized in that one or more catalysts contain 0.1 to 10.0 wt .-% of active component c), based on the total weight of the catalyst. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claims 1 to 6, characterized in that the removal of oxygen from the gases containing one or more ethylenically unsaturated hydrocarbons takes place in a reactor and the gases containing one or several ethylenically unsaturated hydrocarbons have a temperature of ≤ 200 ° C when entering the reactor. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claims 1 to 7, characterized in that the removal of oxygen from the gases containing one or more ethylenically unsaturated hydrocarbons takes place in a reactor and leaving the reactor Gas mixture has a temperature of ≤ 200 ° C has. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claims 1 to 8, characterized in that the ethylenically unsaturated hydrocarbons contain 1 to 8 carbon atoms. Use of catalysts for the removal of oxygen from gases containing one or more ethylenically unsaturated hydrocarbons according to claims 1 to 9, characterized in that the gases contain from 70 to 99.9% by volume of ethylenically unsaturated hydrocarbons, based on the total volume of the hydrocarbon gas.