WO2016083135A1

WO2016083135A1 - Removal of oxygen from hydrocarbon gases

Info

Publication number: WO2016083135A1
Application number: PCT/EP2015/076371
Authority: WO
Inventors: Anne Alber; Marc Eckert; Christoph RÜDINGER
Original assignee: Wacker Chemie Ag
Priority date: 2014-11-28
Filing date: 2015-11-12
Publication date: 2016-06-02
Also published as: DE102014224470A1

Abstract

The present invention provides for the use of catalysts for removal of oxygen from gases comprising one or more ethylenically unsaturated hydrocarbons, characterized in that one or more catalysts comprise, 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, where the active components a), b) and c) are independently in metallic form, in the form of an alloy or in the form of salts.

Description

Removal of oxygen from hydrocarbon gases

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 have naturally gives a limiting degree of purity, for example, oxygen present as an impurity, which is a hindrance in the further use of hydrocarbon gases and should be removed from the hydrocarbon ^¬ material 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 (C0 ₂ ) and water.

The oxidative cleaning is widely used to exhaust called low content of volatile or slightly volatile organic substances, and VOC (Volatile Organic Com ^¬ pounds) to clean. For this purpose, the VOCs are often converted by means of catalytic oxidation to CO ₂ and water. Common Ka ^¬ talysatorsysteme contain as catalytically active species precious metals such as palladium or platinum, which are applied to support, for example on oxidic supports such as Al ₂ O _3, S 1 O _2, lith Zeo-, T 1O ₂ or ZrÜ. ₂ Such oxidation catalysts usually show a "light-off" behavior, ie only from a specifi ^¬ rule temperature, the so-called "light-off" temperature, advertising to the catalysts active. The sales curves are rising around the

"Light-off" temperature jump, and in a relatively narrow temperature range, the turnover increases from 0% to 100%.

Thus van de Beld in Chemical Engineering and Processing 34, (1995), pages 469 to 478 describes 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 is ethene completely converted puts. 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 Ti0 ₂ , I ₂ O ₃ or Si0 ₂ . Pt is recommended as the most suitable catalyst.

Hosseini recommended in Catalysis Today, 122 (2007), pages 391 to 396 for the total oxidation of propylene Pd and Au on T1O ₂ as a catalyst. The light-off temperature is 200 ° C and no CO formation occurs. For the CO oxidation Venezia taught in Applied Catalysis A, 251, (2003), pages 359 to 368 Au-Pd catalysts on Si0 ₂ - From temperatures of> 160 ° C CO can be fully implemented. EP 2656904 Katalysa ^¬ tors for purifying exhaust gases from diesel engines are known. 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 automotive exhaust gases. A problem is the oxidative cleaning especially true if the consist gases to be purified to essential parts of hydrocarbons, especially when keeping the gases additionally significant proportions of oxygen ^¬ ent. For the current catalysts require relatively high temperatures to achieve their catalytic activity or their "light-off" temperature for the oxidation reactions, but especially at relatively high temperatures, undesired byproducts or even decomposition or uncontrolled polymerization of the hydrocarbons can occur. at lower temperatures, in the previously known processes, the oxygen is not sufficiently implemented, and scored no rea ^¬ sponding cleaning action. Against this background, the object was bereitzu ^¬ measures the low adequate removal of oxygen from ethylenically unsaturated hydrocarbons containing gases at as Temperatures, especially at tempera- temperatures <200 ° C, whereby the formation of by-products such as carbon monoxide should be minimized where possible. The present invention is the use of catalysts to remove oxygen from gases, one or more ethylenically unsaturated hydrocarbons containing, characterized in that one or more Katalysa ^¬ factors 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 hydrocarbon preferably containing 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms ^¬. Examples of ethylenically unsaturated Kohlenwasserstof ^¬ Fe 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. Particular preference is given to 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

Vol .-% ethylenically unsaturated hydrocarbons.

The hydrocarbon gases preferably contain 0.1 to 30 vol .-%, more preferably 0.1 to 5 vol .-% and most preferably ^¬ 1 to 3 vol .-% oxygen. The hydrocarbon gas may optionally contain one or more ^¬ re contain other impurities, such as out ^¬ selected from the group comprising nitrogen, carbon dioxide, carbon monoxide and other organic components that are different from the ethyl ^¬ lenisch unsaturated hydrocarbons such as saturated, optionally functionalized Kohlenwasserstof ^¬ fe. Such saturated hydrocarbons contain ^{vorzugswei ¬} se 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 wide ^¬ ren impurities, in the hydrocarbon gases, for example, 0 to 20 Vol .-%, preferably 0 to 5 Vol .-%, particularly preferably 0.01 to 5 Vol .-% and most before ^¬ Trains t to 0 1 to 2 vol .-% included.

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 below in accordance with DIN EN 1839-13. The application of the requirements of DIN EN 1839-13 is familiar to the person skilled in the art.

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, Kali ^¬ order, 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) to Aktivkomponen ^¬ te c) b is preferably from 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),) and c) preferably employed b in the form of their salts in ^¬ play, 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 aluminum silicates, magnesium silicate, magnesium aluminum silicates or zeolites ^¬. Suitable supports are also carbon, carbides or nitrides, for example silicon carbides, boron carbides or boronitrides. Preferred carriers are Si0 ₂ , Al ₂ O ₃ , La ₂ Ü 3, ZrÜ ₂ , MgO, Fe ₂ Ü 3, SnÜ ₂ or Ti0 ₂ . Particularly preferred carriers are S1O ₂ or Al ₂ O ₃ . The most preferred support is pyrogenic Si0 ₂ .

The catalysts may be supported or unsupported. Preferred are supported catalysts. Examples of geträ- siege catalysts are shell or impregnated Kata ^¬ catalysts.

Furthermore, the catalysts may comprise one or more dopants contain substances, for example inorganic salts, such as halo ^¬ halides, oxides, nitrates, nitrites, silicates, carbonates, borates, aluminates, molybdates, tungstates, vanadates, niobates, tantalates, titanates, zirconates or in general polyoxometalates, given ^¬ if 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 can be present in the usual geometries, for example in the form of rings, pellets, cylinders, spheres or monoliths.

The catalysts can be prepared in a manner known per se, as described, for example, in DE 10 2006 058 800 A1, EP 565952, DE 102012003236 A1, WO 2005/065819 A1 or WO 2010 / 056275A1.

For example, the catalysts may be prepared by adding one or more active components and optionally one or several dopants are applied 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 include salts of Aktivkompo ^¬ components, such as their acetates, halides, nitrates, oxides or Hyd ^¬ roxide. The conversion of precursor compounds in Aktivkom- components can be carried out in usual manner, for example by reducing, for example with hydrazine hydrate, formaldehyde, hydrogen, ethene, propene, butene or forming gas as Redukti ^¬ onsmittel. 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 Aktivkom ^¬ components be applied as halides, the halogen may, after application and fixation or reduction of the active components can be reduced halide-content, for example by washing with water or aqueous neutral or alkaline solutions, for example, NH _3, N ₂ H _4, (NH ₄ ) ₂ C0 ₃ , KOH, NaOH, KHC0 ₃ , K ₂ C0 ₃ , NaHC0 ₃ , Na ₂ C0 ₃ , Mg (OAc) ₂ , NaOAc, KOAc. Preference is given here to water. The halide content is preferably -S2000 ppm, more preferably -S1000 ppm and most preferably -S500 ppm.

Preferably, first one or more active components b) and one or more active components c) and optionally one or more dopants and then or applied one or more Ak ^¬ tivkomponenten a) one or more precursor compounds of the active components a) to the support. Preferably, 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 applied several Do ^¬ animal substances on carrier and subsequently transferred to Aktivkom ^¬ 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 more than once, 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 -S 200 ° C, more preferably -S 180 ° C and most preferably -S 160 ° C when entering or just before entering the reactor. The gas mixture leaving the reactor has a temperature of preferably -S 200 ° C, more preferably -S 190 ° C and most preferably -S 180 ° C.

The temperature of the gas mixture leaving the reactor differs from the temperature of the gas mixture entering the reactor by preferably -S 50 ° C, more preferably -S 30 ° C, more preferably -S 25 ° C, even more preferably -S 20 ° C and most preferably -S 15 ° C. The temperature of the reactor temperature control is preferably -S 200 ° C, more preferably -S 190 ° C, and most preferably -S 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 is in the

During the course of the oxidative purification according to the invention was removed from the hydrocarbon gas, and the oxygen of the carbon ^¬ hydrogen gas, which was subjected to the inventive oxidative purification.

After carrying out the removal of oxygen according to the invention, the hydrocarbon gases preferably contain -S 10 vol .-%, more preferably -S 3 vol .-% and most preferably -S 0.01 vol .-% oxygen, each based 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 procedure, the water can additionally be introduced into the reactor material or ^¬ mixed with the to be purified hydrocarbon gas prior to entry into the reactor ge. The amount of hydrogen depends in general ^¬ my then the amount of oxygen in the hydrocarbon gas is hold ent ^¬ and to 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 the sake of clarity, it should be noted that the hydrocarbons In particular, no oxygen is added to the hydrogen gas. Into the reactor to be cleaned Kohlenwas ^¬ hydrogen gas is introduced during the implementation of the purification process thus preferably exclusively.

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. Temperatures for the oxidative purification of hydrocarbon be achieved gases and method are for example carried out at temperatures well below 200 ° C Common platinum or palladium - Surprisingly, this significantly lower with the OF INVENTION ^¬ to the invention catalysts "light-off" could. Oxidation catalysts in this application showed only low oxygen conversions even at temperatures of up to 245 ° C., while with catalysts according to the invention, oxygen conversions of> 90% are possible, for example even at 150 ° C. In addition, the formation of undesirable by-products can be suppressed or even completely ruled out . by-products are, for example carbon monoxide and wide ^¬ re partial oxidation products such as aldehydes, esters, or other hydrocarbons. The included in the hydrocarbon gas Sau ^¬ erstoff can be implemented completely or almost completely 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 heated in an oil-tempered tube reactor

(Length: 2000 mm, inner diameter: 19 mm) with a gas mixture consisting of 98 vol .-% of an ethylenically unsaturated hydrocarbon and 2 vol .-% oxygen fed. The catalytic Gate volume in the tubular reactor was 217 cm. 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):

Ratio of the volume flow (m ³ / h) of the hydrocarbon gas and the reactor volume [m ³ ].

Selectivity:

The quotient of the number of moles of reacted oxygen on the respective product and the number of moles of the total in the reactor set at ^¬ oxygen.

- 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 ~ carrier:

Preparation of the catalyst:

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

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 3,900 1 / h 40% of the initially present in the hydrocarbon gas O ₂ were converted ^¬ sets. In addition to CO ₂ and water, the by-products CO formed with a selectivity of 1% and acetaldehyde with a Selek ^¬ tivity of <1%.

Comparative Example 2

Palladium / gold catalyst on Si0 ₂ ~ carrier:

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 Si0 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 precipitated with a saturated aHC0 ₃ solution. It was again dried at 80 ° C in vacuo (<30 mbar). The precipitation step was repeated again. The catalyst was then treated continuously with demineralized water

(Conductivity <10 yS) washed until the wash water through FAEL ^¬ development reaction with the silver nitrate solution no AgCl precipitation (turbidity of the solution) could be detected any longer. 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, a 0 ₂ -Umsatz reached by 97%. In addition to CO ₂ and water ent ^¬ were no other products.

Example 3:

Palladium / gold catalyst with 2.5 wt .-% potassium as potassium acetate on Si0 ₂ ^~ carrier, based on the total weight of Kata ^¬ lysators:

Preparation of the catalyst:

A solution of 6.44 g of potassium acetate in 90 ml of water was added to 100 g of palladium / gold catalyst on SiO ₂ support from Comparative Example ₂ in a rotary evaporator under rotation. introduced. 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 Si0 _{2 support} , based on the total weight of the catalyst: The catalyst was prepared analogously to Example 3, with the only difference that a solution of 9 g Kaliu ^¬ macetat was used in 90 ml of water.

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 Si0 ₂ ~ carrier, 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%.

Claims

Claims:

1. The use of catalysts for the removal of oxygen from gases containing one or more ethylenically ungesät ^¬-saturated 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 umfas ^¬ send gold and cadmium and

c) contain one or more metals selected from the group umfas ^¬ send 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.

2. The use of catalysts for the removal of oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1, characterized ^¬ characterized marked in that as active component a) is potassium or cesium is used.

3. The use of catalysts for the removal of oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1 or 2, characterized in that a ^¬ is set as the active component c) palladium.

4. The use of catalysts for the removal of oxygen from gases containing one or more ethylenically ungesät ^¬-saturated 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.

5. The use of catalysts for the removal of oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1 to 4, characterized 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 to remove oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1 to 5, characterized in that one or more catalysts 0.1 to 10.0 wt .-% of active component c), based on the total weight of the catalyst.

Use of catalysts to remove oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 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, one or more ethylenically ungesät ^¬-saturated hydrocarbons, when entering the reactor containing have a temperature of <200 ° C.

Use of catalysts to remove oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 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

the gas mixture leaving the reactor has has a Tempe ^¬ temperature of <200 ° C.

Use of catalysts to remove oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1 to 8, characterized in that the ethylenically unsaturated hydrocarbons containing 1 to 8 carbon atoms. Use of catalysts to remove oxygen from gases containing one or more ethylenically ungesät ^¬-saturated hydrocarbons according to claim 1 to 9, characterized in that the gases to from 70 to 99.9 vol .-% ethylenically contain nically unsaturated hydrocarbons based on the total the hydrocarbon gas.