WO2016083135A1 - Élimination de l'oxygène d'hydrocarbures gazeux - Google Patents

Élimination de l'oxygène d'hydrocarbures gazeux Download PDF

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Publication number
WO2016083135A1
WO2016083135A1 PCT/EP2015/076371 EP2015076371W WO2016083135A1 WO 2016083135 A1 WO2016083135 A1 WO 2016083135A1 EP 2015076371 W EP2015076371 W EP 2015076371W WO 2016083135 A1 WO2016083135 A1 WO 2016083135A1
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Prior art keywords
catalysts
oxygen
ethylenically
ungesät
gases containing
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PCT/EP2015/076371
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German (de)
English (en)
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Anne Alber
Marc Eckert
Christoph RÜDINGER
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Wacker Chemie Ag
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Publication of WO2016083135A1 publication Critical patent/WO2016083135A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
    • C07C7/14841—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/106—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • 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
  • 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.
  • VOC Volatile Organic Com ⁇ pounds
  • 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
  • Ethene and propane on Pd catalysts supported on Al 2 O 3 are Pd or Pt on Ti0 2 , I 2 O 3 or Si0 2 . Pt is recommended as the most suitable catalyst.
  • the object was compactzu ⁇ 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
  • hydrocarbon gases 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
  • 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.
  • 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 .-%.
  • 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).
  • active component a) are preferably lithium, sodium, Kali ⁇ order, rubidium, cesium; most preferably potassium and cesium, and most preferably potassium.
  • 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.
  • the active components a) are particularly preferably used in the form of their acetates.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ onsstoff.
  • 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.
  • 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.
  • Precursor compounds of the active components a) applied to the carrier are 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.
  • 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.
  • the temperature of the gas mixture leaving the reactor preferably corresponds to the temperature of the reactor temperature control.
  • 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
  • the degree of conversion denotes the molar ratio of the oxygen which is in the
  • 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.
  • the hydrocarbon gases are thus completely or partially freed of oxygen.
  • 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.
  • no further gas or agent is introduced into the reactor with the hydrocarbon gas to be purified.
  • 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.
  • 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.
  • 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 catalyst given in the respective comparative example or example was heated in an oil-tempered tube reactor
  • 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.
  • Gas mixture consisting of 5% by volume of hydrogen and 95% by volume of nitrogen.
  • the catalyst thus obtained had a platinum content of 1.05 wt. -%.
  • the ethylenically unsaturated hydrocarbon used was ethene.
  • a GHSV of 3,900 1 / h 40% of the initially present in the hydrocarbon gas O 2 were converted ⁇ sets.
  • the by-products CO formed with a selectivity of 1% and acetaldehyde with a Selek ⁇ tivity of ⁇ 1%.
  • the ethylenically unsaturated hydrocarbon used was ethene.
  • 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%.
  • CO 2 and water ent ⁇ were no other products.
  • 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.
  • 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 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 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 Example 5:
  • 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%.

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Abstract

L'invention concerne l'utilisation de catalyseurs pour éliminer l'oxygène de gaz contenant un ou plusieurs hydrocarbures éthyléniquement insaturés. L'invention est caractérisée en ce qu'un ou plusieurs catalyseurs utilisés comme composants actifs contiennent a) un ou plusieurs métaux alcalins, b) un ou plusieurs métaux choisis dans le groupe comprenant l'or et le cadmium, et c) un ou plusieurs métaux choisis dans le groupe comprenant le palladium, le platine, le rhodium, l'iridium et le ruthénium, les composants actifs a), b) et c) étant présents indépendamment les uns des autres sous forme métallique, en tant qu'alliage ou sous forme de sels.
PCT/EP2015/076371 2014-11-28 2015-11-12 Élimination de l'oxygène d'hydrocarbures gazeux WO2016083135A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014224470.6A DE102014224470A1 (de) 2014-11-28 2014-11-28 Entfernung von Sauerstoff aus Kohlenwasserstoffgasen
DE102014224470.6 2014-11-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111905729A (zh) * 2020-07-30 2020-11-10 成都龙飞科技有限公司 一种有机烃类脱氧催化剂及其制备方法
CN115707514A (zh) * 2021-08-19 2023-02-21 中国石油化工股份有限公司 脱氧催化剂及其制备方法和脱除轻质烯烃中氧气的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015213030A1 (de) 2015-07-13 2017-01-19 Wacker Chemie Ag Verfahren zur Entfernung von Sauerstoff aus einem Kohlenwasserstoff und Sauerstoff enthaltenden Gasgemisch

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5764621A (en) * 1980-10-07 1982-04-19 Toa Nenryo Kogyo Kk Removing method of oxygen from gas containing unsaturated hydrocarbon
EP0565952A1 (fr) * 1992-04-08 1993-10-20 Hoechst Aktiengesellschaft Catalyseur sur support, procédé pour sa préparation, ainsi que son utilisation pour préparer l'acétate de vinyle
DE102006058800A1 (de) * 2006-12-13 2008-06-19 Wacker Chemie Ag Verfahren zur Herstellung von Katalysatoren und deren Verwendung für die Gasphasenoxidation von Olefinen
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