EP2872599A1 - Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé - Google Patents

Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé

Info

Publication number
EP2872599A1
EP2872599A1 EP13735333.0A EP13735333A EP2872599A1 EP 2872599 A1 EP2872599 A1 EP 2872599A1 EP 13735333 A EP13735333 A EP 13735333A EP 2872599 A1 EP2872599 A1 EP 2872599A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrocarbons
carbon dioxide
magnesium
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13735333.0A
Other languages
German (de)
English (en)
Inventor
Manfred Baerns
Uwe Rodemerck
Quido Smejkal
Axel BARKSCHAT
Martin HOLENA
David Linke
Martina Marschall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wagner Edmund Dr-Ing
Original Assignee
Wagner Edmund Dr-Ing
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wagner Edmund Dr-Ing filed Critical Wagner Edmund Dr-Ing
Priority to EP13735333.0A priority Critical patent/EP2872599A1/fr
Publication of EP2872599A1 publication Critical patent/EP2872599A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen

Definitions

  • the present invention relates to a method for
  • Presence of a specific catalyst is implemented. With the method according to the invention can be used as fuels
  • Hydrocarbons are formed with very high selectivity. Furthermore arise in the process with good
  • CO2 carbon dioxide
  • global warming global warming
  • CO2 is suitable here as the carbon source, since CO 2 is consumed in the production and only the previously bound amount CO 2 is released when the recovered fuel is combusted.
  • RWGS reverse water-gas shift
  • the RWGS or their reverse reaction is a
  • polymer production In addition to fuel production, the largest consumer of fossil carbon carriers in the chemical industry is polymer production.
  • polymer production predominantly short-chain olefins (ethylene, propylene, butenes) are used as starting materials, from which, directly or after modification, polymers, such as
  • Polyethylene, polypropylene, polyacrylates and polyurethanes are produced mainly from fossil raw materials in refineries by steaming. Other methods, like the
  • CO2 must be stored in underground caverns. However, the CO2 could react with the rock and endanger the stability of the caverns.
  • Iron catalysts which can contain cerium as a promoter were described in S.-S. Nam et al. , J. Chem. Res. (1999) 344 and S.- S. Nam et al. , Appl. Catal. A 179 (1999) 155
  • the object of the invention is a process for producing hydrocarbons and a catalyst therefor
  • Hydrocarbons in particular the chain lengths C5-C15 but also the chain lengths C2-C4 at the highest possible conversion of C0 2 already without recycling of excess CO2 is achieved.
  • a method is sought with which a higher selectivity for liquid C5-C15
  • Hydrocarbons for example, are suitable as fuels, and a higher CC> 2 conversion than with the
  • Catalysts of the prior art for example the 100Fe6, 6Cul5, 7A14K from S.-R. Yan et al. in Appl. Catal. A 194-195 (2000) 63-70.
  • Catalyst contains iron and at least one alkali metal and further satisfies at least one of the following features (i) to (iii):
  • the catalyst contains, based on the
  • Total weight of the catalyst iron in an amount of at least 10% by weight, preferably from 15 to 35% by weight, and further copper and at least one other selected from magnesium, zinc, lanthanum and zirconium;
  • the catalyst comprises TiO 2 and / or a
  • the catalyst further contains ruthenium and / or cobalt.
  • the metals such as iron, alkali metal (eg lithium, sodium and potassium), copper, magnesium, zinc, lanthanum, aluminum, zirconium, manganese, ruthenium and cobalt can also be used as compounds, in particular as Oxides are present.
  • the metals Preferably, at least a portion of the metals, more preferably all metals are present as an oxide.
  • Hydrocarbons of carbon dioxide and hydrogen wherein the carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst contains iron and at least one alkali metal.
  • the at least one alkali metal is advantageously selected from the group consisting of lithium, sodium, potassium and rubidium.
  • the catalyst contains potassium as the at least one alkali metal.
  • the proportion of the at least one alkali metal is 1-30 wt .-% and particularly preferably 5-12 wt .-% with respect to the iron content in
  • the potassium content is preferably 1 to 30 wt .-% and particularly preferably 5 to 12 wt .-% with respect to the iron content in the catalyst.
  • the catalyst comprises 1O2 and / or a
  • the catalyst further contains ruthenium and / or cobalt.
  • the at least one alkali metal contained in the catalyst of process (i) is potassium.
  • the catalyst of process (i) may be two further representatives selected from magnesium, zinc, lanthanum and
  • the catalyst of process (i) may also contain manganese and / or aluminum.
  • the catalyst of process (i) may include manganese and copper.
  • the catalyst contains:
  • Potassium, zirconium and manganese are:
  • a promoter is defined as a constituent or component of a catalyst which positively influences the catalytic reaction.
  • the weight ratio of iron to the total weight of all promoters in the catalyst of process (i) is preferably between 1.5 and 15.
  • the catalyst of process (i) additionally contains ruthenium.
  • the components iron and ruthenium are active components.
  • an active component is defined as the catalytically active ingredient or component.
  • the catalyst of process (i) can be a
  • Catalyst support comprises (unsupported catalyst), the total weight of all promoters in the catalyst based on the catalyst as a whole preferably between 15 and 50 wt .-% and particularly preferably between 30 and 40 wt .-%.
  • Particularly preferred examples of the unsupported catalyst of process (i) are:
  • the metals may be present as oxide and the proportions of the metals in wt .-%, based on the total weight of all metals in metallic form in the catalyst are given.
  • the metals Preferably, at least a portion of the metals, more preferably all metals are present as an oxide.
  • the catalyst support may be selected from the group consisting of Al 2 O 3, Al 2 O 3 MgO, TiC> 2, La 2 O 3, ZrC> 2, ZrC> 2 La 2 C> 3, ZrO 2, SiO 2, zeolites and aluminum -Magnesiumhydroxycarbonaten be selected.
  • AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
  • ZrC> 2-1 ⁇ 203 refers to mixtures of ZrÜ2 and La2Ü3, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : Zr0 2 is between 5:95 and 15:85.
  • Zr0 2 -Si0 2 denotes mixtures of ZrC> 2 and S1O2, where the
  • the weight ratio between Al 2 O 3 and MgO may be arbitrary.
  • the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
  • Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
  • Preferred catalyst supports are 102, Al 2 O 3 and aluminum magnesium hydroxycarbonate, with T1O 2 being particularly preferred.
  • the support materials Al2O3 and T1O2 are advantageous in terms of the yield of C5-C15 hydrocarbons. If 1O2 is used as catalyst support in the catalyst of process (i), a high yield of C5-C15
  • the catalyst support preferably has a particle size of 100 to 250 pm.
  • Process (i) is preferably between 1.5 and 20
  • the supported catalyst of process (i) is
  • catalysts 0.07RuI, 27MgI, 78Cu 20Fe 1.74K / Al 2 O 3 ;
  • the metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of
  • Catalyst and the catalyst support are specified.
  • At least a portion of the metals, more preferably all metals are present as an oxide.
  • Another embodiment of the process according to the invention relates to the use of a catalyst which satisfies feature (ii) (process (ii)). If Ti0 2 or aluminum magnesium hydroxycarbonates are used as catalyst carriers in the catalyst of the process according to the invention, a particularly high yield of valuable metal is obtained
  • Hydrocarbons such as C 2 -C 4 and C 5 -C 15 hydrocarbons, achieved while at the same time little undesirable methane is formed.
  • the catalyst supports TiC> 2 and aluminum magnesium hydroxycarbonates preferably have a particle size of 100 to 250 pm.
  • Total catalyst is preferably between 10 and 50 wt .-% iron, more preferably between 15 and 35 wt .-% iron and most preferably between 20 and 25 wt .-% iron. Due to this high iron content, a particularly high CC> 2 conversion is achieved.
  • the catalyst in process (ii) contains potassium as the at least one alkali metal.
  • the catalyst comprises at least one further member selected from the group consisting of magnesium, zinc, lanthanum, aluminum, zirconium, manganese and copper.
  • the at least one further representative is magnesium, zinc or copper.
  • the catalyst in process (ii) contains potassium and copper and at least one further representative selected from the group consisting of aluminum,
  • Embodiments of process (ii) include
  • the components potassium, copper, magnesium, zinc, lanthanum, zirconium, manganese and aluminum are promoters.
  • the weight ratio of iron to the total weight of all promoters in the catalyst of process (ii) is the weight ratio of iron to the total weight of all promoters in the catalyst of process (ii)
  • Process (ii) is preferably between 1.5 and 20% by weight and more preferably between 3 and 10% by weight, based on the weight of the catalyst as a whole.
  • the catalyst of process (ii) additionally contains ruthenium.
  • the components iron and ruthenium are active components.
  • metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of Total weight of all metals in metallic form in
  • Catalyst and the catalyst support are specified.
  • At least a portion of the metals, more preferably all metals are present as an oxide.
  • a further embodiment of the process according to the invention relates to the use of a catalyst which satisfies feature (iii) (process (iii)).
  • the components are iron, ruthenium and cobalt
  • the catalyst of process (iii) contains potassium as the at least one alkali metal.
  • the catalyst contains at least one further representative, this being selected from the group consisting of magnesium, zinc, lanthanum,
  • Aluminum, zirconium, manganese and copper is selected.
  • the at least one further representative is magnesium, zinc or copper.
  • the catalyst in process (iii) contains potassium and copper and at least one further member selected from the group
  • the catalyst comprises:
  • the components potassium, copper, magnesium, zinc, lanthanum, zirconium, manganese and aluminum are promoters.
  • the weight ratio of iron to the total weight of all promoters in the catalyst of process (iii) is
  • the catalyst in process (iii) may be both supported and unsupported.
  • the total weight of all promoters in the catalyst relative to the catalyst as a whole is preferably between 15 and 50% by weight and more preferably between 30 and 40% by weight.
  • the catalyst support may be selected from the group consisting of Al 2 O 3 , Al 2 O 3 MgO, TiO 2 , La 2 O 3 , ZrO 2 , ZrO 2 La 20 3 , Zr0 2 -Si0 2 , zeolites and aluminum magnesium hydroxycarbonates be selected.
  • AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
  • Mixing ratio can be arbitrary.
  • r02-La2Ü3 denotes mixtures of ZrC> 2 and L .203, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : Zr0 2 is between 5:95 and 15:85.
  • Zr0 2 -Si0 2 denotes mixtures of Zr02 and SXO2, where the
  • the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
  • Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
  • Preferred catalyst supports are iO 2, Al 2 O 3 and aluminum magnesium hydroxycarbonate, with 10O 2 being particularly preferred. These support materials are with regard to the yield of C5- C ] _5 hydrocarbons advantageous.
  • the catalyst support preferably has a particle size of 100 to 250 ⁇ .
  • Process (iii) is preferably between 1.5 and 20% by weight and more preferably between 3 and 10% by weight, based on the weight of the catalyst as a whole.
  • Catalyst and the catalyst support are specified.
  • At least a portion of the metals, more preferably all metals are present as an oxide.
  • process (iv) relates to the preparation of
  • Hydrocarbons of carbon dioxide and hydrogen wherein the carbon dioxide is reacted with hydrogen in the presence of a catalyst, wherein the catalyst contains iron, potassium, copper and magnesium, wherein iron in an amount of
  • At least 8 wt .-% preferably between 10 and 50 wt .-%, particularly preferably between 15 and 35 wt .-%, based on the total weight of the catalyst is included.
  • Catalyst may also contain manganese.
  • the proportion of potassium is 1-30 wt .-% and particularly preferably 5-12 wt .-% with respect to the iron content in the catalyst.
  • the components potassium, copper, magnesium, and manganese are promoters.
  • Iron is an active component
  • the weight ratio of iron to the total weight of all promoters in the catalyst of the process is preferably between 1.5 and 15.
  • the catalyst of the process may comprise a catalyst support on which the active components and promoters
  • the total weight of all promoters in the catalyst based on the catalyst as a whole is preferably between 15 and 50% by weight and
  • the catalyst support can be selected from the group consisting of Al 2 O 3, Al 2 O 3 -MgO, TiC> 2, I 2 O 3, ZrC> 2, ZrC 1 -Cl 2, ZrO 2-SiC> 2, zeolites and Aluminum magnesium hydroxycarbonates be selected.
  • AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
  • Zr02-La2Ü3 denotes mixtures of ZrC> 2 and L .203, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La2Ü3: ZrC> 2 is between 5:95 and 15:85.
  • Zr0 2 -SiC> 2 denotes mixtures of ZrC > 2 and S1O2, where the
  • the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
  • Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
  • the catalyst support is preferably Al 2 O 3.
  • Catalyst support preferably has a particle size of 100 to 250] i.
  • Method is preferably between 1.5 and 20 wt .-% and particularly preferably between 3 and 10 wt .-% based on the weight of the catalyst as a whole.
  • the following catalysts are particularly preferred: 10El, 0Mg 2.0Cu 0.8K / A1 2 0 3
  • Catalyst and the catalyst support are specified.
  • At least a portion of the metals, more preferably all metals are present as an oxide.
  • Another aspect of the invention relates to the use of the catalysts as described above in the process according to the invention, as described, for example, in the attached US Pat
  • Claim 1 is defined.
  • the process of the invention relates to the reaction of carbon dioxide with hydrogen in the presence of a catalyst, i. the hydrogenation of carbon dioxide by hydrogen in the presence of a catalyst
  • the RWGS reaction of carbon dioxide to carbon monoxide takes place and the carbon monoxide formed is converted to hydrocarbons in a Fischer-Tropsch synthesis.
  • the process of the invention may also be referred to generally as a Fischer-Tropsch process. Preferred are the
  • Hydrocarbons C5-C15 hydrocarbons and / or C2-C4 hydrocarbons.
  • the reaction of the carbon dioxide with hydrogen in the process of the invention preferably takes place at a temperature of 150 to 400 ° C, more preferably 300 to 370 ° C, even more preferably 320 ° C to 370 ° C and most preferably 350 ° C , A temperature of 150 to 400 ° C leads to a particularly high yield
  • Hydrocarbons especially C5-C15 hydrocarbons.
  • a temperature of 300 ° C to 350 ° C is particularly suitable in relation to the yield of C5-C15 hydrocarbons.
  • Hydrogen at a pressure of 10 to 50 bar and more preferably between 15 to 30 bar instead.
  • the reaction of the carbon dioxide is carried out with hydrogen at a temperature of 300 ° C and a pressure of 15 bar or at a temperature of 350 ° C and a pressure of 10 bar.
  • the carbon dioxide used in the process according to the invention can be obtained by flue gas separation from the exhaust gas of power plants, which preferably generate electrical energy from fossil fuels.
  • the hydrogen gas used in the process according to the invention can by
  • Hydrocarbons from carbon dioxide and hydrogen can be carried out in a fixed bed, fluidized bed or bubble column reactor.
  • suitable fixed bed reactors are gas-flow fixed bed catalytic reactors,
  • Bubble column reactors and tube bundle reactors. in the A gas-flow catalytic fixed bed reactor according to the invention is preferably used.
  • Hydrogen, water, unreacted carbon dioxide, and carbon monoxide may contain.
  • the carbon monoxide is
  • the product mixture contains C5-C15 and C2-C hydrocarbons. Contain the C2-C4
  • Hydrocarbons C2-C alkanes so they can be dehydrogenated after their separation to C2-C alkenes, especially ethylene, propylene and butenes.
  • c 5 c ⁇ 15 hydrocarbons include linear, branched and cyclic alkanes and alkenes with a chain length of 5 to 15 carbon atoms.
  • Examples of the C5-C15 alkanes are linear, branched and cyclic isomers of pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecans, dodecanes, tridecanes, tetradecanes and pentadecanes.
  • Examples of the 05-015 alkenes include linear, branched and cyclic isomers of pentenes, hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes, tridecenes,
  • the C5-C15 hydrocarbons are preferably linear and / or branched alkanes and alkenes.
  • C2-C4 hydrocarbons include C2-C4 alkanes and C2-C4 alkenes containing from 2 to 4 carbon atoms, where the C4 alkanes and C4 alkenes can be both linear and branched.
  • Examples of the C 2 -C 4 hydrocarbons are ethane, ethylene, propane, propylene, n-butane, isobutane, 1-butene, 2-butene and 2-methyl-1-propene.
  • Butenes include n-butane, isobutane, 1-butene, 2-butene and 2-methyl-1-propene.
  • the hydrocarbons produced are preferably predominantly C 2 -C 15 hydrocarbons, ie those produced
  • Hydrocarbons include C2-C15 hydrocarbons in an amount of at least 50 mol%.
  • the hydrocarbons of the product mixture obtained in the process according to the invention are preferably ⁇ 50 mol%, more preferably ⁇ 70 mol% of C2-C15 hydrocarbons, based on the hydrocarbons produced.
  • Hydrocarbons which are useful, for example, as fuels such as gasoline, diesel and kerosene
  • C2-C hydrocarbons which may be after dehydration as
  • the molar ratio of c is 5 ⁇ 15 c hydrocarbons to C2-C4 hydrocarbons in the product mixture preferably>. 1
  • methane and higher hydrocarbons (with more than 16
  • the product gas is preferably cooled in a phase separator to 35 ° C, thereby to deposit water in liquid form. If necessary, excess carbon dioxide can be removed from the product gas by absorption in a further step.
  • the product gas can be passed through a medium, for example a solvent, which
  • the separated carbon dioxide gas may include the educt gas stream comprising hydrogen gas and carbon dioxide gas in the
  • the product gas can be separated in a cryogenic separation apparatus or by cryogenic separation technique into those components which are liquid or gaseous at room temperature (20 ° C), with a cryogenic heat exchanger being preferred.
  • a cryogenic separation apparatus or by cryogenic separation technique into those components which are liquid or gaseous at room temperature (20 ° C), with a cryogenic heat exchanger being preferred.
  • the C5-C15 As liquids, the C5-C15
  • Hydrocarbons, methane, excess carbon monoxide and hydrogen are obtained in gaseous form.
  • excess hydrogen gas can be recycled by removing methane from the gas mixture of methane, excess carbon monoxide, and hydrogen by means of membrane separation technology or cryogenic separation.
  • the recycled hydrogen gas can then be recycled to the educt gas stream of the process according to the invention
  • the catalyst is reduced with hydrogen before use in the process according to the invention.
  • the catalyst is, for example, at 500 ° C in a
  • Inert gas stream e.g., nitrogen
  • hydrogen e.g., hydrogen
  • the catalyst used in the process of the present invention can be prepared by precipitation from metal salt solutions or by milling metal oxides. This gives an unsupported catalyst.
  • supported catalyst can be prepared by reacting a catalyst support with metal salt solutions, e.g. aqueous metal nitrate solutions, impregnated, for example
  • the impregnated catalyst support is dried after each impregnation step.
  • the catalysts become oxalate during production
  • oxalate is preferably in the form of
  • Ammonium oxalate or metal oxalate is added. Particularly preferred is ammonium oxalate. As has been shown, this leads to a better distribution of the active components, in particular iron, and the promoters in the catalyst or on the support.
  • impregnated catalyst supports are preferably calcined after drying. Calcination may be carried out, for example, in a muffle furnace in still air (e.g., at 350 ° C) or in the inert gas stream (e.g., at 400 ° C). When a catalyst containing oxalate is calcined, complete decomposition (combustion) of the oxalate occurs; the oxalate is removed without residue during calcination.
  • the invention relates to the
  • Catalyst as such.
  • the catalyst according to the invention comprises as
  • Catalyst components based on the total weight of the catalyst, at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from magnesium, zinc, lanthanum and zirconium.
  • the catalyst at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from magnesium, zinc, lanthanum and zirconium.
  • the catalyst based on the total weight of the catalyst, at least 10 wt .-%, preferably 10-50 wt .-%, particularly preferably 15 and 35 wt .-% and very particularly preferably 20-25 wt .-% iron, and potassium, Copper and at least one other component selected from
  • catalyst according to the invention at least one of the following metals: manganese, ruthenium, aluminum and cobalt.
  • Preferred embodiments of the catalyst according to the invention contain
  • the components iron and ruthenium are active components.
  • Magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the catalyst according to the invention is preferably between 1.5 and 15.
  • at least some of the metals are present, more preferably all metals are present as oxide.
  • the catalyst according to the invention can be both supported and unsupported.
  • the total weight of all metals selected from the group consisting of potassium, copper, magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the catalyst based on the total catalyst is preferably between 15 and 50 wt .-% and especially
  • unsupported catalyst of the invention preferably between 30 and 40 wt .-%.
  • Particularly preferred examples of the unsupported catalyst of the invention are: H, 3Lal4, 1Cu70.7 Fe3.9K; and
  • the metals may be present as oxide and the proportions of the metals in wt .-%, based on the total weight of all metals in metallic form in the catalyst are given.
  • the support may be selected from the group consisting of Al 2 O 3 , Al 2 O 3 MgO, TiO 2 , La 2 O 3 , ZrO 2 , ZrO 2 -LaO 3 / ZrO 2 -SiO 2 , zeolites and aluminum magnesium hydroxycarbonates be.
  • AI2O3-MgO refers to mixtures of Al2O3 and MgO, the
  • Zr02-La2Ü3 denotes mixtures of ZrC> 2 and La2Ü3, wherein the mixing ratio can be arbitrary, preferably the weight ratio of La 2 0 3 : ZrC> 2 is between 5:95 and 15:85.
  • Zr0 2 -Si0 2 denotes mixtures of ZrO 2 and S1O2, where the
  • the weight ratio of Al 2 O 3: MgO is between 30:70 (e.g., Pural MG70) and 50:50.
  • Magnesium hydroxycarbonates include amorphous and crystalline forms, among the crystalline forms is hydrotalcite
  • Preferred catalyst supports are TiO 2 ; AI2O3 and aluminum magnesium hydroxycarbonate. These support materials are advantageous in terms of the yield of C5-C15 hydrocarbons. Contains the catalyst T1O2 as a carrier, so is a high yield of C5-C15 hydrocarbons in the
  • Copper, magnesium, zinc, lanthanum, aluminum, zirconium and manganese in the supported catalyst is preferably between 1.5 and 20 wt .-% and particularly preferably between 3 and 10 wt .-% based on the weight of the catalyst as a whole.
  • the supported catalyst of the invention is preferably selected from the following catalysts:
  • the metals may be present as oxide and the proportions of the metals in wt .-%, based on the sum of
  • Catalyst and the carrier are specified.
  • at least a portion of the metals, more preferably all metals are present as an oxide.
  • Another aspect of the invention relates to the use of the catalysts, as described above, in one of
  • Catalyst 2 II, 6Mg II, 6Mn II, 6Cu 58.2Fe 7, OK
  • Catalyst 2 was prepared analogously to the preparation of catalyst 1 from 2.45 g of Mg (NO 3 ) 2 '6H 2 O, 1.06 g of Mn (NO 3 ) 2 .4 ⁇ 2 0, 0.88 g of Cu (NO 3 ) 2 -3H 2 0, 7.81 g Fe (NO 3 ) 3 .9H 2 0 and 0.36 g K 0 3
  • Step 1 5 ml of an aqueous Fe (NO 3 ) 3 solution (content 48.7 g / 1 Fe) were added to lg Ti0 2 (Degussa Aerolyst 7708, particle size 0.1-0, 25 mm) while shaking at room temperature.
  • aqueous Fe (NO 3 ) 3 solution content 48.7 g / 1 Fe
  • Step 2 5 ml of an aqueous KNO 3 solution (content 3.69 g / 1 K) were pipetted onto the dried mixture from step 1 with shaking at room temperature, the mixture was heated to 100 ° C. and concentrated by shaking at 100 ° C. and dried , Step 3: To the dried mixture of Step 2 was added 5 ml of an aqueous under stirring at room temperature
  • Step 4 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
  • Catalyst 4 was prepared analogously to the preparation of catalyst 3, wherein in step 2, the content of the aqueous K O3 solution was 4.85 g / 1 K.
  • Catalyst 5 0, lRu 0.2Cu 0.3Zn 19.2Fe 1.3K / TiO;
  • Catalyst 5 was prepared analogously to the preparation of catalyst 3, wherein in step 1, the content of the aqueous
  • step 4 the content of the aqueous K O 3 solution was 3.41 g / 1 K
  • step 3 the content of the aqueous Zn (NO 3) 2 solution 0.71 g / 1 Zn, and step 4 was replaced by the following steps 4 through 6:
  • Step 4 To the dried mixture of step 3, shaking at room temperature 5 ml of an aqueous
  • Step 5 To the dried mixture from step 4, shaking at room temperature, 5 ml of an aqueous
  • Step 6 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
  • Catalyst 6 0.07Ru 0.3Zn 19.2Fe 2, OK / Tip
  • Catalyst 6 was prepared analogously to the preparation of catalyst 3, wherein in step 1, the content of the aqueous
  • step 4 the content of the aqueous KNO 3 solution was 5.13 g / 1 K
  • step 3 the content of the aqueous Zn (NO 3) 2 solution was 0 , 73 g / 1 Zn
  • step 4 was replaced by the following steps 4 and 5:
  • Step 4 To the dried mixture of step 3, shaking at room temperature 5 ml of an aqueous
  • Step 5 The dried mixture was calcined for 5 hours in a muffle furnace at 350 ° C in air.
  • Catalyst 7 2.2Zr l, 7Mn 2.4Zn 18.8Fe 1.6K / TiO ?
  • Catalyst 7 was prepared analogously to the preparation of catalyst 5, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.3 g / 1 Fe, in step 2 the content of the aqueous KNO 3 solution was 4.37 g / 1 K in step 3, the content of the aqueous n (NO 3) 2 solution was 6.68 g / 1 Zn, in step 4, the content of the aqueous ZrO (NO 3) 2 solution was 5.91 g / 1 Zr and in step 5, the content of the aqueous Mn (NC> 3) 2 solution was 4.62 g / 1 Mn.
  • Catalyst 8 0.97Cu 19.16Fe 1.63K / Tip ?
  • Catalyst 8 was prepared analogously to the preparation of catalyst 3, wherein in step 1 5 ml of an aqueous solution of Fe (NC> 3) 3 (content 49.1 g / 1 Fe) and 2 ml of a
  • Ammonium oxalate solution (content 25.15 g / 1 oxalate) were used, in step 2 the content of the aqueous KNO3 solution was 4.17 g / 1 K and in step 3 the content of the aqueous Cu (N0 3 ) 2 solution 2, 48 g / 1 Cu.
  • Catalyst 9 was prepared analogously to the preparation of catalyst 6, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.2 g / 1 Fe, in step 2 the content of the aqueous KNO 3 solution was 4.42 g / 1K, in Step 3, the content of the Cu (NO3) 2 aqueous solution was 10.24 g / 1Cu, and in Step 4, the content of the ZrO (NO3) 2 aqueous solution was 5.71 g / 1Zr.
  • Catalyst 10 3, lZr 2, 8Mn 0.9Cu 18.8Fe 1.4K / Tip ?
  • Catalyst 10 was prepared analogously to the preparation of catalyst 5, wherein in step 1 the content of the aqueous Fe (NO 3) 3 solution was 51.5 g / 1 Fe, in step 2 the content of the aqueous KNC> 3 solution was 3.80 g / 1 K was, in step 3, the content of the aqueous ZrO (NO 3) 2 solution was 8.43 g / 1 Zr, in step 4, the content of the aqueous Mn (NO 3) 2 solution was 7.62 g / 1 Mn and in step 5, the content of the aqueous Cu (NC> 3) 2 solution was 2.57 g / l Cu.
  • Hydrogen was carried out in a fixed bed reactor (stainless steel tube, Inner diameter 5 mm). All catalysts were used in a grain fraction of 100-250 ⁇ m to
  • the analysis of the product gas was carried out by an on-line coupled Gas Chromatograph in the gas phase. For this purpose, an operating pressure of 10 bar was chosen and, secondly, all the pipes and valves after the reactor and the GC inlet system were heated to at least 150 ° C. In addition, a hot gas separator (150 ° C) and a cold gas separator (room temperature), each with integrated aerosol filter, were integrated into the flue pipe. It became the two-dimensional
  • thermal conductivity detector CO2, ethylene, ethane, water, H2, N2, methane, CO
  • FID Flame ionization detector
  • Gas chromatographs were equipped with a PorapakQ column and a PoraPlotQ column. The columns were heated with a temperature program from the start temperature 50 ° C to 200 ° C.
  • the second channel was equipped with a FFAP column and an Al203 / KCl column (25m x 0.32mm, 5pm film thickness) with the FFAP column operating at a temperature of 50-200 ° C.
  • the A ⁇ Oß / KCl column was washed with a
  • Olefin content proportion of C2-C4 olefins in mol% based on all the C2-C4 hydrocarbons (Y (C 2 -C 4))
  • the catalysts 11-67 were prepared by impregnation of carrier materials. If several components are contained on a carrier, the impregnation became sequential,
  • Aerolyst 7708 Aerolyst 7708), S1O2 (Degussa Aerolyst 355), aluminum magnesium hydroxycarbonate with a weight ratio A1 2 0 3 : MgO of 30: 70 (Pural MG70)
  • Table 2 summarizes the compositions of catalysts 11-67. The proportion of the respective metal in metallic form is given in wt .-% and refers to the total weight of all metals in metallic form in the catalyst and the catalyst support. Table 2: Compositions of the catalysts
  • Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
  • Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
  • Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.
  • Oxalate was used in the preparation of the catalyst, but in the composition of the calcined catalyst, oxalate is not included.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène selon lequel on fait réagir le dioxyde de carbone avec l'hydrogène en présence d'un catalyseur spécial. Le procédé selon l'invention permet de former comme carburants (essence, diesel, kérosène) d'intéressants hydrocarbures C5-C15 avec une sélectivité très élevée. Des hydrocarbures C2-C4 qui peuvent être utilisés comme substances de départ de valeur dans l'industrie chimique se forment dans le procédé avec une bonne sélectivité. Dans le procédé, on obtient déjà une conversion élevée de CO2 sans recyclage de dioxyde de carbone excédentaire. L'invention concerne, selon un autre aspect, les catalyseurs proprement dits.
EP13735333.0A 2012-07-13 2013-07-12 Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé Withdrawn EP2872599A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13735333.0A EP2872599A1 (fr) 2012-07-13 2013-07-12 Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP12176417.9A EP2684936A1 (fr) 2012-07-13 2012-07-13 Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé
EP13735333.0A EP2872599A1 (fr) 2012-07-13 2013-07-12 Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé
PCT/EP2013/064806 WO2014009534A1 (fr) 2012-07-13 2013-07-12 Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé

Publications (1)

Publication Number Publication Date
EP2872599A1 true EP2872599A1 (fr) 2015-05-20

Family

ID=48782366

Family Applications (2)

Application Number Title Priority Date Filing Date
EP12176417.9A Withdrawn EP2684936A1 (fr) 2012-07-13 2012-07-13 Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé
EP13735333.0A Withdrawn EP2872599A1 (fr) 2012-07-13 2013-07-12 Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP12176417.9A Withdrawn EP2684936A1 (fr) 2012-07-13 2012-07-13 Procédure de fabrication d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et d'un catalyseur utilisable dans le procédé

Country Status (3)

Country Link
US (1) US20150197462A1 (fr)
EP (2) EP2684936A1 (fr)
WO (1) WO2014009534A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019123251A1 (fr) * 2017-12-18 2019-06-27 King Abdullah University Of Science And Technology Catalyseurs pour l'hydrogénation du co2
FI128568B (en) * 2018-06-11 2020-08-14 Teknologian Tutkimuskeskus Vtt Oy Method and apparatus for the formation and use of hydrocarbons
CN113117683A (zh) * 2021-04-16 2021-07-16 郑州大学 负载型催化剂及其制备方法
CN113797955B (zh) * 2021-10-25 2023-04-04 中国华能集团清洁能源技术研究院有限公司 一种二氧化碳加氢制低碳烯烃的催化剂及其制备方法
JP2024075191A (ja) * 2022-11-22 2024-06-03 本田技研工業株式会社 二酸化炭素還元触媒装置、二酸化炭素還元方法、及び触媒の製造方法
CN117019151B (zh) * 2023-07-05 2024-04-12 珠海市福沺能源科技有限公司 一种二氧化碳加氢的空腔微球催化剂及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100351625B1 (ko) * 1999-11-11 2002-09-11 한국화학연구원 탄화수소 제조용 촉매
CN1159098C (zh) * 2001-07-12 2004-07-28 中国科学院山西煤炭化学研究所 一种费托合成用铁基催化剂及其制备方法
CN101293206B (zh) * 2008-04-21 2010-09-22 神华集团有限责任公司 一种费托合成用铁基催化剂及其制备方法
US8658554B2 (en) * 2009-11-04 2014-02-25 The United States Of America, As Represented By The Secretary Of The Navy Catalytic support for use in carbon dioxide hydrogenation reactions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2014009534A1 *

Also Published As

Publication number Publication date
US20150197462A1 (en) 2015-07-16
EP2684936A1 (fr) 2014-01-15
WO2014009534A1 (fr) 2014-01-16

Similar Documents

Publication Publication Date Title
EP2872599A1 (fr) Procédé de production d'hydrocarbures à partir de dioxyde de carbone et d'hydrogène et un catalyseur utilisable dans le procédé
Naik et al. Synthesis of DME from CO2/H2 gas mixture
Zhang et al. Zn and Na promoted Fe catalysts for sustainable production of high-valued olefins by CO2 hydrogenation
Malyaadri et al. Synthesis of glycerol carbonate by transesterification of glycerol with dimethyl carbonate over Mg/Al/Zr catalysts
Lindström et al. Activity and characterization of Cu/Zn, Cu/Cr and Cu/Zr on γ-alumina for methanol reforming for fuel cell vehicles
Prieto et al. New insights into the role of the electronic properties of oxide promoters in Rh-catalyzed selective synthesis of oxygenates from synthesis gas
Inui Highly effective conversion of carbon dioxide to valuable compounds on composite catalysts
CA2744628C (fr) Procede de fabrication de methanol, d'oxyde de dimethyle et d'olefines legeres a partir de gaz de synthese
Olivier et al. Oxidative coupling of methane using catalyst modified dense perovskite membrane reactors
Langfeld et al. Comparison of oxidizing agents for the oxidative coupling of methane over state-of-the-art catalysts
EP3515882B1 (fr) Nouveaux procédés respectueux de l'environnement hautement efficaces permettant de convertir des flux riches en co2 ou en co en combustibles liquides et en produits chimiques
US8378152B2 (en) Method of producing propylene glycol
CN103127935B (zh) 一种介孔碳负载型铜基催化剂、其制备方法及其应用
Tsai et al. The synthesis of hydrocarbons and oxygenates during CO hydrogenation on CoCuZnO catalysts: Analysis at the site level using multiproduct SSITKA
Ramirez et al. Multifunctional catalyst combination for the direct conversion of CO2 to propane
CN108176405A (zh) 一种烷烃脱氢反应增强助剂及其制备方法和应用
Gianotti et al. Hydrogen generation via catalytic partial dehydrogenation of gasoline and diesel fuels
WO2012031341A1 (fr) Procédé de production d'hydrogène à partir de l'éthanol
Wang et al. Catalytic activity for direct CO2 hydrogenation to dimethyl ether with different proximity of bifunctional Cu-ZnO-Al2O3 and ferrierite
Narayanan et al. Nickel-alumina prepared by constant and varying pH method: Evaluation by hydrogen-oxygen chemisorption and aniline hydrogenation
CA2747085A1 (fr) Variation de l'impregnation en etain d'un catalyseur pour la deshydrogenation d'alcanes
Heracleous et al. Bio-oil upgrading via vapor-phase ketonization over nanostructured FeO x and MnO x: Catalytic performance and mechanistic insight
Zhang et al. Highly efficient ZnCeZrOx/SAPO-34 catalyst for the direct conversion of CO2 into light olefins under mild reaction conditions
EP2832716A1 (fr) Synthèse de 1,3-butadiène
Wang et al. Preparation and catalytic property of Pb-Zr mixed oxides for methyl phenyl carbonate disproportionation to synthesize diphenyl carbonate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150130

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170201