Patent Application
20220184586
Described herein is a hydrogenation catalyst, and precursor thereof and its use in a process suitable for the conversion of carbon dioxide and/or carbon monoxide into hydrocarbons. In particular, the catalysts and processes described herein yield C5+ hydrocarbons, in particular C5+ alpha olefins.
Olefins are extensively used in the chemical industry as building blocks for manufacturing a wide range of products and as a main component of fuels. Alpha-olefins have a double bond at the terminal or alpha position which enhances the reactivity of this position and renders them useful in the production of detergents, lubricants, plasticizers, drugs, fine chemicals and polymers.
The catalytic preparation of hydrocarbons from synthesis gas (“syngas”) is well known and is commonly referred to as the Fischer-Tropsch synthesis. However, Fischer-Tropsch synthesis tends to favour the formation of saturated hydrocarbon paraffins.
Furthermore, the need to reduce greenhouse gases (GHGs) emissions from the transportation sector is well known. The UK decreased GHG emissions from road transport by 8.6% between 2002-2012 due to increasing fuel efficiency, hydrogen fuel cells and electric vehicles. However, aviation, the second largest transportation subsector, increased its emissions by about 6%.
Fuel production from CO2 or CO may address the preceding energy demands whilst meeting environmental standards. However, state-of-the-art CO2-to-fuel conversion yields mainly C1 products (syngas, formic acid, methanol), and less frequently, C2-C4 products, such as mixed alcohols and olefins. These processes, followed by Methanol-To-Olefin (MTO) or FT synthesis, can yield long-chain hydrocarbon mixtures. However, it is particularly challenging to derive fuel, such as jet fuel, directly via such routes because they fail to produce the desired composition (i.e. comprising C5+ hydrocarbons) to meet stringent, well-established standards.
There is a need for new, high performance catalysts and processes suitable for the conversion of carbon dioxide and/or carbon monoxide to hydrocarbons. In particular inexpensive and abundant catalysts are required and processes using said catalysts which improve the conversion of carbon dioxide and/or carbon monoxide, and/or improve the yield of valuable hydrocarbons, such as C5+ hydrocarbons, including C5+ (alpha) olefins.
In a first aspect, the present invention relates to a catalyst precursor comprising an iron species, an alkali metal or salt thereof, and a complexing agent.
In a second aspect, the present invention relates to a process for the preparation of a catalyst precursor comprising:
In a third aspect, the present invention relates to a catalyst precursor obtainable according to the process of the second aspect.
In a fourth aspect, the present invention relates to a catalyst obtainable by activation of a catalyst precursor according to the first aspect.
In a fifth aspect, the present invention relates to a process for preparing a catalyst comprising:
(a) providing a catalyst precursor according to the first or third aspect of the invention;
(b) optionally subjecting said catalyst precursor to calcination; and
(c) activating said precursor.
In a sixth aspect, the present invention relates to a catalyst obtainable according to the process of the fifth aspect.
In a seventh aspect, the present invention relates to a process for the hydrogenation of carbon dioxide comprising contacting a feedstock comprising hydrogen and carbon dioxide with a catalyst precursor according to the first aspect or a catalyst according to the fourth or sixth aspects at elevated temperature and pressure.
In an eighth aspect, the present invention relates to a process for the hydrogenation of carbon monoxide comprising contacting a feedstock comprising hydrogen and carbon monoxide with a catalyst precursor according to the first aspect or a catalyst according to the fourth or sixth aspect at elevated temperature and pressure.
In a ninth aspect, the present invention relates to a process for the production of olefins comprising contacting a feedstock comprising hydrogen and carbon dioxide and/or carbon monoxide with a catalyst precursor according to the first aspect or a catalyst according to the fourth or sixth aspects at elevated temperature and pressure.
In a tenth aspect, the present invention relates to a process for the production of a fuel comprising contacting a feedstock comprising hydrogen and carbon dioxide and/or carbon monoxide with a catalyst precursor according to the first aspect or a catalyst according to the fourth or sixth aspects at elevated temperature and pressure.
In an eleventh aspect, the present invention relates to a heterogeneous mixture comprising a catalyst precursor according to the first aspect or a catalyst according to the fourth or sixth aspect and a gas comprising hydrogen and carbon monoxide, and/or hydrogen and carbon dioxide.
Preferred, suitable, and optional features of any one particular aspect of the present invention are also preferred, suitable, and optional features of any other aspect.
As used herein the term “catalyst precursor” refers to a material used in the preparation of a catalytically active species. Typically, the precursor is prepared by calcination of the components thereof. Typically, the catalyst precursor will require conversion to the catalytically active species, for instance by oxidation, reduction and/or heat treatment, or a combination thereof. Suitably, activation is via reduction. The catalyst precursor may be converted in the catalytically active species (i.e. “activated”) in-situ (i.e. under the reaction conditions) or the catalyst precursor may also be converted to the catalytically active species prior to addition to the reaction.
As used herein the term “liquid” refers to a material which is liquid at standard ambient temperature and pressure (SATP), i.e. at a temperature of 298.15 K (25° C.) and at 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm).
As used herein the term “hydrocarbon” refers to organic compounds consisting of carbon and hydrogen.
For the avoidance of doubt, hydrocarbons include straight-chained and branched, saturated and unsaturated aliphatic hydrocarbon compounds, including alkanes, alkenes, and alkynes, as well as saturated and unsaturated cyclic aliphatic hydrocarbon compounds, including cycloalkanes, cycloalkenes and cycloalkynes, as well as hydrocarbon polymers, for instance polyolefins.
Hydrocarbons also include aromatic hydrocarbons, i.e. hydrocarbons comprising one or more aromatic rings. The aromatic rings may be monocyclic or polycyclic.
Aliphatic hydrocarbons which are substituted with one or more aromatic hydrocarbons, and aromatic hydrocarbons which are substituted with one or more aliphatic hydrocarbons, are also of course encompassed by the term “hydrocarbon” (such compounds consisting only of carbon and hydrogen) as are straight-chained or branched aliphatic hydrocarbons that are substituted with one or more cyclic aliphatic hydrocarbons, and cyclic aliphatic hydrocarbons that are substituted with one or more straight-chained or branched aliphatic hydrocarbons.
A “Cn-m hydrocarbon” or “Cn-Cm hydrocarbon” or “Cn-Cm hydrocarbon”, where n and m are integers, is a hydrocarbon, as defined above, having from n to m carbon atoms. For instance, a C5-1s hydrocarbon is a hydrocarbon as defined above which has from 5 to 16 carbon atoms, a C5+ hydrocarbon is a hydrocarbon as defined above which has 5 or more carbon atoms etc.
The term “alkane”, as used herein, refers to a linear or branched chain saturated hydrocarbon compound. Examples of alkanes, are for instance, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane and tetradecane. Alkanes such as dimethylbutane may be one or more of the possible isomers of this compound. Thus, dimethylbutane includes 2,3-dimethybutane and 2,2-dimethylbutane. This also applies for all hydrocarbon compounds referred to herein including cycloalkane, alkene, cycloalkene.
The term “cycloalkane”, as used herein, refers to a saturated cyclic aliphatic hydrocarbon compound. Examples of cycloalkanes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane. Examples of a C5-8 cycloalkane include cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, dimethylcyclopentane and cyclooctane. The terms “cycloalkane” and “naphthene” may be used interchangeably.
The term “alkene”, as used herein, refers to a linear or branched chain hydrocarbon compound comprising one or more carbon-carbon double bonds. Examples of alkenes are butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene and tetradecene. Alkenes typically comprise one or two double bonds. The terms “alkene” and “olefin” may be used interchangeably. The one or more double bonds may be at any position in the hydrocarbon chain. The alkenes may be cis- or trans-alkenes (or as defined using E- and Z-nomenclature). An alkene comprising a terminal double bond may be referred to as an “alk-1-ene” (e.g. hex-1-ene), a “terminal alkene” (or a “terminal olefin”), or an “alpha-alkene” (or an “alpha-olefin”). The term “alkene”, as used herein also often includes cycloalkenes.
The term “cycloalkene”, as used herein, refers to partially unsaturated cyclic hydrocarbon compound. Examples of a cycloalkene includes cyclobutene, cyclopentene, cyclohexene, cyclohexa-1,3-diene, methylcyclopentene, cycloheptene, methylcyclohexene, dimethylcyclopentene and cyclooctene. A cycloalkene may comprise one or two double bonds.
The term “aromatic hydrocarbon” or “aromatic hydrocarbon compound”, as used herein, refers to a hydrocarbon compound comprising one or more aromatic rings. The aromatic rings may be monocyclic or polycyclic. Typically, an aromatic compound comprises a benzene ring. An aromatic compound may for instance be a C6-14 aromatic compound, a C6-12 aromatic compound or a C6-10 aromatic compound. Examples of C6-14 aromatic compounds are benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, naphthalene, methylnaphthalene, ethylnaphthalene and anthracene.
As used herein “metal species” is any compound comprising a metal. As such, a metal species includes the elemental metal, metal oxides and other compounds comprising a metal, i.e. metal salts, alloys, hydroxides, carbides, borides, silicides and hydrides. When a specific example of a metal species is stated, said term includes all compounds comprising that metal, e.g. iron species includes elemental iron, iron oxides, iron salts, iron alloys, iron hydroxides, iron carbides, iron borides, iron silicides and iron hydrides for instance.
As used herein, the term “heterogeneous mixture” refers to the physical combination of at least two different substances wherein the two different substances are not in the same phase. For instance, one substance may be a solid and one substance may be a liquid or gas.
In one aspect, the present invention relates to a catalyst precursor comprising at least one iron species, an alkali metal or salt thereof and a complexing agent.
In one embodiment, the present invention relates to a catalyst precursor comprising iron or a salt, oxide or hydroxide thereof, an alkali metal or salt thereof, and a complexing agent.
In one embodiment, the complexing agent is suitable for complexing metal cations, in particular iron cations. Accordingly, suitable complexing agents comprise one or more functional groups selected from carboxylic acids, hydroxyl groups, amide groups or amino groups. Suitably, the complexing agent comprises two or more functional groups selected from carboxylic acids, hydroxyl groups, amide groups or amino groups. Suitably the complexing agent is an organic compound.
In one embodiment, the complexing agent or organic compound is selected from a hydroxycarboxylic acid, an aminocarboxylic acid, multicarboxylic acids or salts thereof. Suitably, the complexing agent or organic compound is selected from a hydroxycarboxylic acid and a multicarboxylic acid, or a salt thereof. Alternatively, the complexing agent or organic compound is selected from a hydroxycarboxylic acid and an aminocarboxylic acid, or a salt thereof.
In one embodiment, the complexing agent or organic compound is a bi- or multi-dentate hydroxycarboxylic acid or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from glycolic acid, lactic acid, hydracylic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, mandelic acid, citric acid, sugar acids, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, tannic acid, succinic acid, salicylic acid, glutaric acid, adipic acid, glycine, hippuric acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), alanine, valine, leucine and isoleucine, and salts thereof.
In one embodiment, the complexing agent or organic compound is selected from glycolic acid, lactic acid, hydracylic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, mandelic acid, citric acid, sugar acids, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, tannic acid, succinic acid, salicylic acid, glutaric acid, adipic acid, hippuric acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from hydroxybutyric acid, hydroxyvaleric acid, malic acid, mandelic acid, citric acid, sugar acids, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, tannic acid, succinic acid, salicylic acid, glutaric acid, adipic acid, hippuric acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from hydroxybutyric acid, hydroxyvaleric acid, malic acid, mandelic acid, citric acid, sugar acids, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, tannic acid, succinic acid, salicylic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from citric acid, sugar acids, tartaric acid, oxalic acid, salicylic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from citric acid, sugar acids, tartaric acid, oxalic acid, salicylic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
In one embodiment, the complexing agent or organic compound is selected from citric acid, tartaric acid, oxalic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof. Suitably, the complexing agent is citric acid.
In one embodiment, the complexing agent to metal molar ratio is about 0.4:1 to about 4:1. Suitably, the complexing agent to metal molar ratio is about 0.5:1 to about 2:1.
In one embodiment, the complexing agent to metal molar ratio is about 0.8:1 to about 4:1. Suitably, the complexing agent to metal molar ratio is about 1:1 to about 3:1.
In one embodiment, the complexing agent to metal molar ratio is about 0.5:1 to about 5:1. Suitably, the complexing agent to metal molar ratio is about 0.8:1 to about 2:1.
In one embodiment, the complexing agent to iron molar ratio is about 0.5:1 to about 5:1. Suitably, the complexing agent to iron molar ratio is about 0.8:1 to about 2:1.
In one embodiment, the iron species is selected from elemental iron, an iron salt, an iron oxide, an iron alloy, an iron hydroxide, an iron carbide, an iron boride, an iron silicide and an iron hydride. Suitably, the iron species is selected from elemental iron, an iron salt, an iron alloy, an iron hydroxide, and an iron silicide. More suitably, the iron species is selected from elemental iron, an iron salt and an iron hydroxide.
In one embodiment, the iron species is an iron salt. In one embodiment, the iron salt is an iron nitrate, an iron sulphate, an iron halide (suitably iron chloride), or an iron organic acid salt. Suitably, the iron salt is iron (III) nitrate or iron (II) nitrate.
In another embodiment, the iron species is iron powder. The skilled person would understand that iron powder is a commercially available form of elemental iron.
In another embodiment, the iron species is iron oxide, suitably Fe3O4.
In one embodiment, the catalyst precursor comprises from about 5 to about 90 wt. % Fe. Suitably, the catalyst precursor comprises about 10 to about 90 wt. % of Fe. Suitably, from about 15 to about 90 wt. % of Fe, more suitably from about 20 to about 90 wt. % of Fe, more suitably from about 25 to about 90 wt. % of Fe, more suitably from about 30 to about 90 wt. % of Fe, more suitably from about 40 to about 90 wt. % of Fe, more suitably from about 50 to about 90 wt. % of Fe.
In one embodiment, the catalyst precursor comprises from about 5 to about 80 wt. % Fe. Suitably, the catalyst precursor comprises about 10 to about 80 wt. % of Fe. Suitably, from about 15 to about 80 wt. % of Fe, more suitably from about 20 to about 80 wt. % of Fe, more suitably from about 25 to about 80 wt. % of Fe, more suitably from about 30 to about 80 wt. % of Fe, more suitably from about 40 to about 80 wt. % of Fe, more suitably from about 50 to about 80 wt. % of Fe.
In another embodiment, the catalyst precursor comprises from about 10 to about 90 wt. % Fe. Suitably, the catalyst precursor comprises about 10 to about 80 wt. % of Fe. Suitably, from about 10 to about 70 wt. % of Fe, more suitably from about 10 to about 65 wt. % of Fe.
In another embodiment, the catalyst precursor comprises from about 10 to about 80 wt. % Fe. Suitably, the catalyst precursor comprises about 10 to about 70 wt. % of Fe. Suitably, from about 10 to about 60 wt. % of Fe, more suitably from about 10 to about 50 wt. % of Fe.
In one embodiment, the alkali metal is selected from potassium, sodium, lithium or caesium. Accordingly, the catalytic precursor may comprise a potassium, sodium, lithium or caesium, or a salt thereof. Suitably, the alkali metal is present as a salt. Suitably, the alkali metal is an alkali metal carbonate, such as potassium carbonate, sodium carbonate, caesium carbonate, lithium carbonate.
In one embodiment, the catalyst precursor comprises from about 0.5 to about 30 wt. % of alkali metal. Suitably, the catalyst precursor comprises about 0.5 to about 25 wt. % of alkali metal. Suitably, from about 0.5 to about 20 wt. % of alkali metal, more suitably from about 0.5 to about 15 wt. % of alkali metal, more suitably from about 0.5 to about 10 wt. % of alkali metal, more suitably from about 0.5 to about 5 wt. % of alkali metal.
In one embodiment, the catalyst precursor comprises from about 1 to about 30 wt. % of alkali metal. Suitably, the catalyst precursor comprises about 1 to about 25 wt. % of alkali metal. Suitably, from about 1 to about 20 wt. % of alkali metal, more suitably from about 1 to about 15 wt. % of alkali metal, more suitably from about 1 to about 10 wt. % of alkali metal, more suitably from about 1 to about 5 wt. % of alkali metal.
In one embodiment, the catalyst precursor may comprise further metal species. Suitably, these further metals will act as promotors in the catalytically active material. In one embodiment, the further metal species is a transition metal species. Suitably, the further metal species is a transitional metal, or salt, oxide or hydroxide thereof.
Suitably, the catalyst precursor further comprises cobalt, chromium, copper, iridium, manganese, molybdenum, palladium, platinum, rhenium, rhodium, ruthenium, strontium, tungsten, vanadium, zinc, or a salt, oxide or hydroxide thereof.
In another embodiment, the catalyst precursor further comprises cobalt, copper, manganese, zinc or a salt, oxide or hydroxide thereof.
In one embodiment, the catalyst precursor comprises manganese oxide.
In one embodiment, the catalyst precursor comprises manganese nitrate.
In one embodiment, the catalyst precursor comprises from about 1 to about 50 wt. % of a further metal species. Suitably, the catalyst precursor comprises about 1 to about 40 wt. % of a further metal species.
In another embodiment, the catalyst precursor comprises from about 5 to about 30 wt. % of a further metal species, more suitably from about 5 to about 20 wt. % of a further metal species, more suitably from about 5 to about 15 wt. % of a further metal species, more suitably from about 5 to about 15 wt. % of a further metal species.
In one embodiment, the catalyst precursor comprises from about 1 to about 30 wt. % of a further metal species. Suitably, the catalyst precursor comprises about 1 to about 25 wt. % of a further metal species. Suitably, from about 1 to about 20 wt. % of a further metal species, more suitably from about 1 to about 15 wt. % of a further metal species, more suitably from about 1 to about 10 wt. % of a further metal species, more suitably from about 1 to about 5 wt. % of a further metal species.
In one embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn, Zn, Cu and Co or a salt, oxide or hydroxide thereof, an alkali metal or salt thereof and a complexing agent.
In one embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn, Zn, Cu and Co or a salt, oxide or hydroxide thereof, an alkali metal or salt thereof and an organic compound.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn and Co or a salt, oxide or hydroxide, an alkali metal or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn and Co or a salt, oxide or hydroxide, an alkali metal or salt thereof and an organic compound.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, a further transition metal selected from Mn and Co or a salt, oxide or hydroxide, an alkali metal or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, a further transition metal selected from Mn and Co or a salt, oxide or hydroxide, an alkali metal or salt thereof and an organic compound.
In another embodiment, the catalyst precursor comprises an iron salt, a manganese salt, an alkali metal or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises an iron salt, a manganese salt, an alkali metal or salt thereof and an organic compound.
In another embodiment, the catalyst precursor comprises an iron powder, a manganese salt, a cobalt salt, an alkali metal or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises an iron powder, a manganese salt, a cobalt salt, an alkali metal or salt thereof and an organic compound. In another embodiment, the catalyst precursor comprises an iron nitrate, a manganese nitrate, an alkali metal or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises an iron nitrate, a manganese nitrate, an alkali metal or salt thereof and an organic compound.
Suitably, the alkali metal is potassium. Accordingly, in one embodiment, the catalyst precursor comprises iron or a salt or oxide thereof, at least one further transition metal selected from Mn, Zn, Cu and Co or a salt or oxide thereof, potassium or salt thereof, and a complexing agent.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn and Co or a salt, oxide or hydroxide, potassium or salt thereof and a complexing agent.
In another embodiment, the catalyst precursor comprises iron or a salt, oxide or hydroxide thereof, at least one further transition metal selected from Mn and Co or a salt, oxide or hydroxide, potassium or salt thereof and an organic compound.
Suitably, the complexing agent or organic compound is as defined in one of the afore-mentioned embodiments. Suitably, the cobalt salt is cobalt nitrate. Suitably, the manganese salt is manganese nitrate.
In one embodiment, the catalyst precursor comprises iron (II or III) nitrate, manganese (II) nitrate, potassium carbonate and citric acid. In another embodiment, the catalyst precursor essentially consists of iron (II or III) nitrate, manganese (II) nitrate, potassium carbonate and citric acid.
In another embodiment, the catalyst precursor comprises iron powder, manganese (II) nitrate, cobalt nitrate, sodium carbonate and citric acid. In another embodiment, the catalyst precursor essentially consists of iron powder, manganese (II) nitrate, cobalt nitrate, sodium carbonate and citric acid
In one embodiment, the catalyst precursor comprises (i) Fe or a salt thereof, (ii) Mn or a salt thereof, (iii) K or a salt thereof and (iv) citric acid or a salt thereof.
In one embodiment, the catalyst precursor comprises (i) Fe or a salt thereof, (ii) Mn or a salt thereof, (iii) Co or a salt thereof (iii) K or a salt thereof and (iv) citric acid or a salt thereof.
Suitably, the molar ratio of Fe:Mn is between about 100:1 to about 4:1, more suitably about 15:1 to about 5:1.
Suitably, the molar ratio of Fe:K is about 100:1 to about 2:1; more suitably, the molar ratio of Fe:K is about 20:1 to about 4:1, more suitably about 10:1 to about 2:1.
Suitably, the molar ratio of (Fe+Mn+K):citric acid is between about 5:1 to 0.5:1, suitably about 2:1 to about 1:1.
Suitably, the molar ratio of Fe:Co is about 40:1 to about 10:1, more suitably about 30:1 to about 10:1, more suitably about 20:1.
In a second aspect, the present invention relates to a process for the preparation of a catalyst precursor comprising:
In this aspect, the iron species, alkali metal or salt thereof, and the complexing agent may be as defined in any of the afore-mentioned embodiments.
In one embodiment, the solvent comprises water. Suitably, the solvent is water.
Step (a) may further comprise the addition of one or more further metal species, suitably, a further transition metal species. In one embodiment, a further transition metal selected from Mn, Zn, Co and Cu, or a salt, oxide or hydroxide thereof is combined in step (a).
In step (b) the mixture may be agitated by any means known in the art, such as stirring, shaking, vortexing and sonicating.
In step (c) the mixture is suitably heated to a temperature of from about 30° C. to 120° C., more suitably about 30° C. to about 80° C., more suitably about 50° C.
The process may further comprise a further step (d) wherein the slurry or paste of step (c) is calcined to provide a powder. Suitably, the calcination is performed at a temperature of between about 300 to about 500° C., more suitably about 350° C. Suitably the calcination is performed in air, suitably static air. Typically, the calcination will result in combustion of organic components of the precursor.
The process may further comprise step (e) wherein the calcined powder is ground or milled, for instance, in order to reduce the particle size.
In another aspect, the present invention relates to a process for the preparation of a catalyst precursor comprising:
In one embodiment, step (a) may further comprise the addition of one or more further metal species. In one embodiment, at least one further transition metal selected from Mn, Zn, Co and Cu, or a salt, oxide or hydroxide thereof is combined in step (a). Suitably, Mn or a salt, oxide or hydroxide thereof and Co or a salt, oxide or hydroxide thereof is further combined in step (a).
In step (b) the agitation may be by any means known in the art, such as stirring, shaking, milling and grinding.
In one embodiment, the process for the preparation of a catalyst precursor comprises:
In another aspect, the present invention relates to a catalyst obtainable by activating a catalyst precursor obtainable according to a process described herein, or catalyst obtainable by activating a catalyst precursor described herein.
Suitably, the catalyst is suitable for the hydrogenation of carbon dioxide and/or carbon monoxide.
In one embodiment, the catalyst comprises an iron carbide, suitably Fe5C2.
In one embodiment, the catalyst comprises an iron carbide, at least one further transition metal selected from Mn, Zn, Cu and Co or a salt, oxide or hydroxide thereof, an alkali metal or salt thereof.
In another embodiment, the catalyst comprises an iron carbide, at least one further transition metal selected from Mn and Co or a salt, oxide or hydroxide, and an alkali metal or salt thereof.
In another embodiment, the catalyst precursor comprises an iron carbide, manganese or oxide thereof, and an alkali metal.
In another embodiment, the catalyst comprises an iron carbide, a manganese or an oxide thereof, cobalt or an oxide thereof, and an alkali metal.
Suitably, the alkali metal is potassium.
In another embodiment, the catalyst comprises an iron carbide, at least one further transition metal selected from Mn and Co or an oxide thereof, and potassium.
Suitably, the iron carbide is Fe5C2.
Suitably, the molar ratio of Fe:Mn is between about 100:1 to about 4:1, more suitably about 15:1 to about 5:1.
Suitably, the molar ratio of Fe:K is about 100:1 to about 2:1; more suitably, the molar ratio of Fe:K is about 20:1 to about 4:1, more suitably about 10:1 to about 2:1.
Suitably, the molar ratio of Fe:Co is about 40:1 to about 10:1, more suitably about 30:1 to about 10:1, more suitably about 20:1.
In another aspect, the present invention relates to a process for preparing a catalyst comprising:
(a) providing a catalyst precursor as defined in any of the above-mentioned embodiments
(b) optionally subjecting said catalyst precursor to calcination; and
(c) activating said precursor.
In one embodiment, the catalyst is suitable for hydrogenation of carbon dioxide and/or carbon monoxide.
Suitably, the calcination is performed at a temperature of between about 100° C. to about 500° C., or about 250° C. to about 500° C., more suitably about 300° C. to about 350° C. Suitably the calcination is performed in air, suitably static air. Typically, the calcination will result in decomposition or partial combustion of organic components of the precursor.
Step (b) may further comprise grinding or milling the calcined powder in order to reduce the particle size.
The calcined material of step (b) or the precursor of step (a) may be activated, for instance by reduction. Suitably, the material to be activated is exposed to a mixture of CO and hydrogen gas at a temperature of about 250° C. to about 500° C., more suitably about 300 to about 350° C.
In one aspect, the present invention relates to a process for the hydrogenation of carbon dioxide comprising contacting a feedstock comprising hydrogen and carbon dioxide with a catalyst precursor or a catalyst as defined herein at elevated temperature and pressure.
In another aspect, the present invention relates to a process for the hydrogenation of carbon monoxide comprising contacting a feedstock comprising hydrogen and carbon monoxide with a catalyst precursor or a catalyst as defined herein at elevated temperature and pressure.
In another aspect, the present invention relates to a process for the production of olefins comprising contacting a feedstock comprising (i) hydrogen and (ii) carbon dioxide and/or carbon monoxide, with a catalyst precursor or a catalyst as defined herein at elevated temperature and pressure.
Suitably, the olefins are C5+ olefins, or alpha olefins, or linear olefins. More suitably the olefins are C5+ alpha olefins. Suitably the olefins are liner alpha olefins. More suitably, the olefins are C5+ linear alpha olefins.
Suitably, the olefins are C5-16 olefins. More suitably the olefins are C5-16 alpha olefins. More suitably, the olefins are C5-16 linear alpha olefins.
In another aspect, the present invention relates to a process for the production of hydrocarbons comprising contacting a feedstock comprising (i) hydrogen and (ii) carbon dioxide and/or carbon monoxide, with a catalyst precursor or a catalyst as defined herein at elevated temperature and pressure.
Suitably, the hydrocarbons are C5+ hydrocarbons, more suitably C8-C18 hydrocarbons, more suitably C8-C16 hydrocarbons. In one embodiment, the hydrocarbons are C8-C18 alkanes, more suitably C8-C16 alkanes. In one embodiment, the hydrocarbons are jet fuel range hydrocarbons.
In another aspect, the present invention relates to a process for the production of a fuel comprising contacting a feedstock comprising (i) hydrogen and (ii) carbon dioxide and/or carbon monoxide, with a catalyst precursor or a catalyst as defined herein at elevated temperature and pressure.
Suitably, the fuel is selected from gasoline, diesel and aviation/jet fuel.
In conducting carbon monoxide or carbon dioxide hydrogenation or olefin production, the catalyst or catalyst precursor is charged into a reaction zone. The catalyst having been activated ex situ (for instance by heating, or if required by oxidation and subsequent reduction with syngas or hydrogen). The catalyst precursor may be activated in situ, for instance, under the conditions of the reaction.
The catalyst may be used in a fixed bed, a moving bed, ebulating bed, fluidized bed, or slurry bed reactor. Suitably, the catalyst is used in a fixed bed reactor.
In one embodiment, when CO hydrogenation is desired, the feedstock comprising a mixture of hydrogen and carbon monoxide, at suitable H2:CO molar ratio, is contacted with the bed of catalyst, and reacted at reaction conditions. Generally, the molar ratio of H2:CO ranges from about 0.4:1 to about 6:1, suitably from about 0.5:1 to about 3:1, more suitably about 1:1 to about 2:1.
In another embodiment, when CO2 hydrogenation is desired, the feedstock comprising a mixture of hydrogen and carbon dioxide, at suitable H2:CO2 molar ratio, is contacted with the bed of catalyst, and reacted at reaction conditions. Generally, the molar ratio of H2:CO2 ranges from about 0.4:1 to about 8:1, suitably about 0.4:1 to about 6:1, suitably from about 0.5:1 to about 5:1, more suitably about 1:1 to about 4:1. Suitably, the molar ratio of H2:CO2 ranges from about 0.5:1 to about 4:1, more suitably about 1:1 to about 3:1.
The reaction temperatures are elevated. As used herein elevated temperature is a temperature which is elevated with respect to standard ambient temperature, i.e. a temperature of 298.15 K (25° C.). In one embodiment, the feedstock is contacted with the catalyst precursor or catalyst at a temperature of about 180° C. to about 500° C., suitably from about 250° C. to about 500° C., more suitably about 280° C. to about 350° C., or about 300° C. to about 350° C.
The reaction pressures are elevated. As used herein elevated pressure is a pressure which is elevated with respect to standard ambient pressure, i.e. a pressure of 100,000 Pa (1 bar, 14.5 psi, 0.9869 atm). In one embodiment, the feedstock is contacted with the catalyst precursor or catalyst at a pressure of about 500 KPa to about 10 MPa, suitably about 500 KPa to about 5 MPa, suitably about 500 KPa to about 2 MPa, suitably about 1 MPa. The invention will now further be described by means of the following numbered paragraphs:
1. A catalyst precursor comprising an iron species (suitably iron or a salt, oxide or hydroxide thereof) an alkali metal or salt thereof and a complexing agent.
2. A catalyst precursor according to paragraph 1 wherein the complexing agent comprises one or more functional groups selected from carboxylic acids, hydroxyl groups, amide groups or amino groups.
3. A catalyst precursor according to paragraph 1 wherein the complexing agent comprises one or more functional groups selected from carboxylic acids, hydroxyl groups, and amide groups.
4. A catalyst precursor according to paragraph 1 wherein the complexing is selected from a hydroxycarboxylic acid, an aminocarboxylic acid and multicarboxylic acids or salts thereof.
5. A catalyst precursor according paragraph 1 wherein the complexing agent is selected from glycolic acid, lactic acid, hydracylic acid, hydroxybutyric acid, hydroxyvaleric acid, malic acid, mandelic acid, citric acid, sugar acids, tartronic acid, tartaric acid, oxalic acid, malonic acid, maleic acid, tannic acid, succinic acid, salicylic acid glutaric acid, adipic acid, glycine, hippuric acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (N-(2-Hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), alanine, valine, leucine and isoleucine, and salts thereof.
6. A catalyst precursor according paragraph 1 wherein the complexing agent is selected from citric acid, tartaric acid, oxalic acid, EDTA (ethylenediaminetetraacetic acid), NTA (nitroilotiracetic acid), DTPA (diethylenetriaminepentaacetic acid), and HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid), or a salt thereof.
7. A catalyst precursor according to any one of the preceding paragraphs wherein the complexing agent is citric acid and/or salt thereof.
8. A catalyst precursor according to any one of the preceding paragraphs wherein the alkali metal is selected from potassium, sodium, lithium and caesium.
9. A catalyst precursor according to any one of the preceding paragraphs wherein the alkali metal is selected from potassium, sodium and caesium.
10. A catalyst precursor according to any one of the preceding paragraphs wherein the alkali metal is potassium.
11. A catalyst precursor according to any one of the preceding paragraphs wherein the iron species is an iron nitrate salt, suitably iron (II) nitrate or iron (III) nitrate.
12. A catalyst precursor according to any one of paragraphs 1 to 10 wherein the iron species is selected from elemental iron, an iron oxide, an iron salt or iron hydroxide, suitably wherein the iron species is iron powder.
13. A catalyst precursor according to any one of the preceding paragraphs comprising a further metal species.
14. A catalyst precursor according to paragraph 13 wherein the further metal species is present at about 1 to about 20 wt. %.
15. A catalyst precursor according to any one of the preceding paragraphs further comprising one or more transition metals selected from Mn, Zn, Co and Cu, or salts, oxides or hydroxides thereof.
16. A catalyst precursor according to paragraph 15 wherein the transition metal is selected from Mn and Co, or salts, oxides and hydroxides thereof.
17. A catalyst precursor according to any one of the preceding paragraphs comprising (i) Fe or a salt thereof, (ii) Mn or a salt thereof, (iii) K or a salt thereof and (iv) citric acid or a salt thereof.
18. A catalyst precursor according to paragraph 17 further comprising (v) Co or a salt thereof.
19. A catalyst precursor according to any one of paragraphs 1 to 11 and 13 to 17 comprising iron (III) nitrate, manganese (II) nitrate, potassium carbonate and citric acid.
20. A catalyst precursor according to any one of paragraphs 1 to 10 and 12 to 18 comprising iron powder, manganese (II) nitrate, cobalt nitrate, sodium carbonate and citric acid.
21. A catalyst precursor according to any one of the preceding paragraphs wherein the molar ratio of Fe:alkali metal is about 100:1 to about 4:1; suitably about 20:1 to about 4:1, more suitably about 10:1.
22. A catalyst precursor according to any one of the preceding paragraphs wherein the complexing agent to Fe molar ratio is about 1:1 to about 3:1.
23. A catalyst precursor according to any one of paragraphs 15 to 20 wherein the molar ratio of Fe:Mn is between about 100:1 to about 4:1, suitably about 10:1.
24. A catalyst precursor according to any one of paragraphs 15 to 20 wherein the molar ratio of (Fe+Mn+K):citric acid is between about 5:1 to 0.5:1, suitably about 2:1 to about 1:1.
25. A catalyst precursor according to any one of paragraphs 15, 16, 18 and 20 wherein the molar ratio of Fe:Co is about 40:1 to about 10:1, more suitably about 30:1 to about 10:1, more suitably about 20:1.
26. A process for the preparation of a catalyst precursor comprising:
All catalyst component materials were obtained from commercial sources as indicated below and used without further modification.
The general method for preparation of the catalyst utilized an organic combustion method. Typically, iron salt and alkali metal salts were mixed with complexing agent in the desired ratios and stirred in water to provide a homogenous aqueous solution. The solution was heated at about 50° C. for 1 to 2 hours to obtain a slurry. The slurry is then ignited in a furnace at about 350° C. in static air for 4 hours to provide a catalyst precursor.
For instance, preparation of a Fe—Mn—K catalyst comprised mixing citric acid monohydrate with iron (III) Nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, wherein the molar ratio of citric acid:(Fe+Mn+K) was about 2, and weight ratio of (Fe and Mn and K-precursors+citric acid)/water was about 2:1. The mixture was stirred to form a homogeneous aqueous solution, and heated at 50° C. for 1-2 hours to obtain a citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
The carbon dioxide hydrogenation experiments are carried on in a fixed bed reactor (
After reduction, the temperature is decreased to about 50° C., and a mixture of H2/CO2 (3:1) and N2 (as an internal standard) is used as feedstock gas. Gas flow is set to 40 mL/min (GSVH=2400 mL/g cat). The N2 was added as inert gas in the syngas feedstock for the conversion calculation. As the mass flow of N2 doesn't change before and after the reaction, the CO2 and H2 conversion, CO and CnHm selectivity can be calculated as set out below.
The reactor is heated at a heating rate of 2° C./min until reaction temperature (about 300° C. to 320° C.). The reaction pressure is controlled at 10 bar (1 Mpa) by a back pressure regulator.
The gaseous products are analyzed on a Perkin Elmer Clarus GC and the collected liquid products are analysed by GC-MS.
The CO2 and H2 conversion, and products selectivity are calculated by the following equations:
Table 1 provides examples of Fe—Mn—K catalysts with varying ratios of Fe:Mn:K prepared as set out above with citric acid as the complexing agent. The H2 and CO2 conversion, and products selectivity over the different catalysts after reaction as set out above for a reaction time of 20 hours are shown in Table 1.
Table 2 and
Table 2 and
The XRD Patterns of each of the catalysts were recorded on Bruker D8 ECO X-ray diffractometer using graphite monochromatized Cu Ka radiation (λ=0.15418 nm over 2θ range from 20-80° at a scan rate of 0.02°/s). Most of peaks can be assigned to Fe3O4.
The crystallites sizes are calculated with the Debye-Scherrer formula based on the peaks of 2θ=35.9°:
Where β is the full-width at half-maximum (FWHM) value of XRD diffraction lines, the wavelength λ=0.15418 nm and θ is the half diffraction angle of 2θ. The catalysts showed small crystallites sizes (Table 3), around 10 nm, which are in accordance with the broad peaks in XRD spectrums (
In order to study the effects of various promotors on the CO2 hydrogenation, iron based catalysts were prepared with potassium and various promotors. The catalysts were prepared using an organic combustion method similar to that described above with citric acid as the complexing agent. The catalyst precursors of the catalysts studied in Table 4 were prepared as follows:
Example 4: citric acid monohydrate and iron (III) nitrate nonahydrate molar ratio of 2:1 were dissolved in water to form a homogeneous aqueous solution (weight of (iron(III) nitrate nonahydrate+citric acid monohydrate) to water of about 2:1), and heated at 50° C. for 1-2 hours to obtain a citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 5: citric acid monohydrate, iron (III) nitrate nonahydrate, and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:K of 100:10, and the molar ratio of citric acid:(Fe+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+potassium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 6: citric acid monohydrate, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of citric acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 7: citric acid monohydrate, iron (III) nitrate nonahydrate, zinc nitrate hexahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Zn:K of 100:10:10, the molar ratio of citric acid:(Fe+Zn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+zinc nitrate hexahydrate+potassium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 8: citric acid monohydrate, iron (III) nitrate nonahydrate, copper(II) nitrate trihydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Cu:K of 100:10:10, the molar ratio of citric acid:(Fe+Cu+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+copper(II) nitrate trihydrate+potassium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a catalyst powder.
Catalyst performance was assessed in CO2 hydrogenation as described above with a reaction time of 20 hours.
Table 4 shows the effect of the inclusion of transition metal (TM) promotors in the catalysts. Catalysts were prepared using citric acid as the complexing agent and had a molar ratio of K:Fe and TM:Fe of 1:10 where applicable. In Table 4, the column titles for the hydrocarbons have the following meanings: C2-4=: C2-C4 olefin, C2-40: C2-C4 paraffin; C5+: liquid products; C5-16=: C5-C16 olefin.
Table 5 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
The XRD Patterns (
In order to study the effects of various alkali metals on the CO2 hydrogenation, iron based catalysts were prepared with a manganese promotor and the alkali metal varied between Na, K and Cs. The catalyst was prepared using an organic combustion method similar to that described above. The catalyst precursors of the catalysts studied in Table 7 were prepared as follows:
Example 9: citric acid monohydrate, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and sodium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:Na of 100:10:10, the molar ratio of citric acid:(Fe+Mn+Na) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+sodium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 10: citric acid monohydrate, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of citric acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a catalyst powder.
Example 11: citric acid monohydrate, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and caesium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:Cs of 100:10:10, the molar ratio of citric acid:(Fe+Mn+Cs) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+caesium carbonate+citric acid)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Catalyst performance was assessed in CO2 hydrogenation as described above with a reaction time of 20 hours.
Table 7 shows the effect of the inclusion of alkali metals (AM) in the catalysts. Catalysts were prepared using citric acid as the complexing agent and had a molar ratio of AM:Fe and Mn:Fe of 1:10. In Table 7, the column titles for the hydrocarbons have the following meanings: C2-4=: C2-C4 olefin, C2-40: C2-C4 paraffin; C5+: liquid products; C5-16=: C5-C16 olefin.
Table 8 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
The XRD Patterns (
In order to study the effects of the complexing agent used in the preparation of the catalysts on the catalyst performance, a series of iron based catalysts were prepared using a variety of complexing agents. The catalysts included potassium and manganese in a molar ratio to Fe of 1:10. The catalysts were prepared using an organic combustion method similar to that described above. The catalyst precursors of the catalysts studied in Table 10 were prepared as follows:
Example 12 (reference): iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate)/water was about 2:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain a water free mixture. This mixture is calcinated at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 13: urea, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of urea:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+urea)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain urea based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 14: tannic acid, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of tannic acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+tannic acid)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain tannic acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 15: Ethylenediaminetetraacetic acid (EDTA), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of EDTA:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+EDTA)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain an EDTA based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 16: citric acid, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of citric acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+citric acid)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain citric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a catalyst powder.
Example 17: glycine, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of glycine:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+glycine)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain glycine based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 18: oxalic acid, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of oxalic acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+oxalic acid)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain oxalic acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 19: Nitrilotriacetic acid (NTA), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of NTA:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+NTA)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain NTA based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 20: Diethylenetriaminepentaacetic acid (DTPA), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of DTPA:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+DTPA)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain DTPA based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 21: tartaric acid, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of tartaric acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+tartaric acid)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain tartaric acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 22: Hydroxyethylethylenediaminetriacetic Acid (HEDTA), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of HEDTA:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+HEDTA)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain HEDTA based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 23: salicylic acid, iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the molar ratio of Fe:Mn:K of 100:10:10, the molar ratio of salicylic acid:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+salicylic acid)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain salicylic acid based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 24: sugar (commercial granulated sugar), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous solution, wherein the weight ratio of Fe:Mn:K of 100:10:10, the molar ratio of sugar:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+sugar)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain sugar based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Example 25: flour powder (commercial white wheat flour (plain flour or self-raising flour)), iron (III) nitrate nonahydrate, manganese(II) nitrate tetrahydrate and potassium carbonate, were dissolved in water to form a homogeneous aqueous slurry, wherein the weight ratio of Fe:Mn:K of 100:10:10, the molar ratio of flour:(Fe+Mn+K) was about 2, and weight ratio of (iron (III) nitrate nonahydrate+manganese(II) nitrate tetrahydrate+potassium carbonate+flour powder)/water was about 1:1. The mixture was stirred, and heated at 50° C. for 1-2 hours to obtain flour based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Catalyst performance was assessed in CO2 hydrogenation as described above with a reaction time of 20 hours.
Table 10 shows that effect of the complexing agent used in the preparation of the catalysts on performance. In Table 10, the column titles for the hydrocarbons have the following meanings: C2-4=: C2-C4 olefin, C2-40: C2-C4 paraffin; C5+: liquid products; C5-16=: C5-C16 olefin.
Table 11 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
The XRD Patterns (
The iron based catalysts prepared with complexing agent and with the addition of Na, K and/or Cs improved selectivity of olefin production in the CO2 hydrogenation reaction. The further addition of Mn, Zn and/or Cu promotors also showed high selectivity for olefins over paraffins. Different organic compounds were applied as the complexing agent during the catalyst preparation. The catalysts prepared with citric acid, EDTA, oxalic acid, NTA, DTPA, Tartaric acid, HEDTA showed highest selectivity for olefins. The catalysts can also be applied for the production of fuels (gasoline, diesel, aviation fuel/jet fuel) via CO2 and/or CO hydrogenation.
All catalyst component materials were obtained from commercial sources as indicated below and used without further modification.
Typically, catalysts were prepared using iron powder as the iron source. Iron powder, cobalt nitrate, manganese nitrate, alkali metal salts (e.g. potassium, sodium carbonate, lithium carbonate, caesium carbonate) were mixed together, and the mixture was ground to uniformity, the complexing agent (citric acid) was added to the mixture (suitably in about a 1:1 weight ratio with iron), and the mixture ground once more to uniformity. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder to provide a catalyst precursor.
Prior to the reaction, the catalyst precursor was reduced in syngas (H2:CO=2:1 or 1:1) at atmospheric pressure, with a GHSV (gas hourly space velocity) of 1000 mL/g hrs, at 320° C. for 32 hours, the heating rate at 5° C./min to provide the activated catalyst.
After reduction, the temperature is decreased to less than 50° C., and a mixture of H2/CO (1:1) and N2 (as an internal standard) is used as feedstock gas. Gas flow is set to 40 mL/min (GSVH=2 400 mL/g cat). The N2 was added as inert gas in the syngas feedstock for the conversion calculation. As the mass flow of N2 doesn't change before and after the reaction, the CO and H2 conversion, CO2 and CnHm selectivity can be calculated as set out below.
The reactor (
The gaseous products are analyzed on a Perkin Elmer Clarus GC and the collected liquid products are analysed by GC-MS.
The CO and H2 conversion, and products selectivity are calculated by the following equations:
Table 13 studies the effect of adding a further transition metal, cobalt, to Fe—Mn—Na catalysts. The reaction time, H2 and CO conversion, and product selectivity over the different catalysts after reaction as set out above are shown in Table 13.
The catalyst precursors of the catalysts studied in Table 13 were prepared as follows:
Examples 26-30: Iron powder, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Mn:Na of 100:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 31-35: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 10:2:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 36-44: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 45-50: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:8:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 51-55: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:10:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Table 14 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
Table 15 studies the effect various alkali metals on the CO hydrogenation. Iron based catalysts were prepared with a manganese and a cobalt promotor and the alkali metal varied between Na, K and Li. The catalysts were prepared using a method similar to that described above. The catalyst precursors of the catalysts studied in Table 15 were prepared as follows:
Examples 56-65: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, lithium carbonate were mixed together with molar ratio of Fe:Co:Mn:Li of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder was 1:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 66-70: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder was 1:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 71-76: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, potassium carbonate were mixed together with molar ratio of Fe:Co:Mn:K of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 1:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Table 16 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
Table 17 studies the effect of manganese loading on the CO hydrogenation. Iron based catalysts were prepared with a manganese and a cobalt promotor and sodium. The catalysts were prepared using a method similar to that described above. In particular, the catalyst precursors of the catalysts of Table 17 were prepared as follows:
Examples 76-80: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 1:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Examples 81-88: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:5:20:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 1:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into catalyst powder.
Table 18 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
Table 19 studies the effect of feedstock composition on the CO hydrogenation. Iron based catalysts were prepared with a manganese and a cobalt promotor and sodium. The catalysts were prepared using a method similar to that described above. The reaction was performed using syngas with varying ratios of H2:CO.
The catalyst precursors of the catalysts of Table 19 were prepared as follows:
Examples 89-110: Iron powder, cobalt (II) nitrate hexahydrate, manganese (II) nitrate tetrahydrate, sodium carbonate were mixed together with molar ratio of Fe:Co:Mn:Na of 100:5:10:2, and the mixture was ground to uniformity, citric acid was added to the mixture and the mixture ground once more to uniformity, wherein the weight ratio of citric acid to iron powder of 4:1. The obtained mixtures were dried at 80° C. for 24 hours. The dried mixtures (without calcination) were ground into powder.
Table 20 provides the molar ratio of olefins:paraffins for the C2-C4 hydrocarbons produced.
Tables 21 and 22 study CO hydrogenation under a variety of conditions using a Fe—Co—Mn—Na catalyst (100:5:20:2). The GC-MS spectrum showing the product profile of example 111 is shown in
Iron powder has applied as iron source with a complexing agent to prepare catalysts. The preparation does not require calcination thus saving energy and reducing emissions. The prepared catalysts show high CO conversion, low CH4 selectivity, high olefin selectivity, and stability. The addition of alkali metal and optionally transition metals (e.g. Co, Mn) promoted the olefin selectivity, both in gaseous and liquid products. The catalysts can also be used for the production of fuels (gasoline, diesel, aviation/jet fuel) at a higher H2:CO molar ratio in feedstock.
The catalysts prepared for CO2 hydrogenation also can be applied in the CO hydrogenation and vice versa.
Jet fuel or aviation fuel are used in gas-turbine engines to power aircraft. The main components of jet fuel are linear and branched alkanes and cycloalkanes with a typical carbon chain-length distribution of C8-C18, and preferably with a carbon chain length distribution of C8-C16.
The generation of the jet fuel range hydrocarbons in the product of CO2 hydrogenation using catalysts disclosed herein.
Catalysts were prepared by the organic combustion method. A Fe—Mn—K catalyst precursor was prepared by mixing citric acid monohydrate (99%, Sigma-Aldrich) with iron (III) nitrate nonahydrate (98%, Sigma-Aldrich), manganese(II) nitrate tetrahydrate (97%, Sigma-Aldrich) and potassium nitrate (99%, Sigma-Aldrich). The molar ratio of citric acid:(Fe+Mn+K) was 2, and weight ratio of (Fe- and Mn- and K-precursors+citric acid):water was 2:1. The mixture was stirred to form a homogeneous aqueous solution, and heated at 50° C. for 1 to 2 hours to obtain a citric acid-based slurry. This paste is ignited at 350° C. (furnace temperature) in static air for 4 hours to produce a powder.
Catalysts with different transition metal (Mn, Cu, Zn) promoters were also prepared using the same method, the catalysts of Fe—Cu—K and Fe—Zn—K were prepared with transition metal precursors of copper (II) nitrate trihydrate (99-104%, Sigma-Aldrich), and zinc nitrate hexahydrate (98%, Sigma-Aldrich) respectively.
Catalysts with different base metal promoters of Fe—Mn—Li, Fe—Mn—Na, and Fe—Mn—Cs were prepared with precursors of lithium carbonate (99%, Sigma-Aldrich), sodium carbonate (99.6%, Acros Organics), cesium carbonate (99%, Sigma-Aldrich) respectively.
In each case, the molar ratio of Fe:transition metal:base metal was 10:1:1.
Fe—Mn—K catalysts were also prepared using organic compounds other than citric acid, the organic compounds used as urea (Bio-Reagent, Sigma-Aldrich), tannic acid (ACS reagent, Sigma-Aldrich), Ethylenediamine Tetraacetic Acid (EDTA, 99.5%, Fisher Scientific), oxalic acid (99.0%, Sigma-Aldrich), Nitrilotriacetic acid (NTA, 99%, Sigma-Aldrich), Diethylenetriaminepentaacetic acid (DTPA, 98%, Sigma-Aldrich), tartaric acid (99.5%, Sigma-Aldrich), N-(2-Hydroxyethyl) ethylenediamine-N,N′,N′-triacetic acid (HEDTA, 98%, Sigma-Aldrich), salicylic acid (99.0%, Sigma-Aldrich). The catalysts were prepared with citric acid as the organic compound unless otherwise stated.
CO2 hydrogenation experiments were carried out in a fixed bed reactor as previously described. Prior to the reaction, the catalyst precursor was in situ reduced with syngas (H2:CO=2:1) at atmospheric pressure, with a GHSV (gas hourly space velocity) of 1000 mL g−1 hr−1, at 320° C. for 24 hours. After the reactor temperature cooling down to below 50° C., and the mixture of gas with an H2/CO2 ratio of 3 and N2 (as an internal standard gas) was introduced into the reactor, the gas flow of 40 mL min−1 (GSVH=2 400 mL g−1 hr−1). The reactor was heated with a heating rate of 2° C./min until the reaction temperature (300° C.). The reaction pressure was fixed at 10 bar (1 MPa) by a back pressure regulator.
The effluent gaseous products were analysed on an online Gas Chromatograph (Perkin Elmer Clarus 580 GC) with flame ionization detector (FID) and thermal conductivity detector (TCD) detectors, the collected liquid products were analysed by Gas Chromatograph Mass Spectrometer (SHIMADZU GCMS-QP2010 SE).
The CO2 and H2 conversion, products selectivity were calculated as previously described.
The powder X-ray diffraction (XRD) analyses of catalysts used a Cu Kα (0.15418 nm) X-ray source (25 kV, 40 mA) on a Bruker D8 Advance diffractometer. Diffraction patterns were recorded over a 10-80° 29 angular range using a step size of 0.016°. Crystallite sizes were determined using the Scherrer equation.
X-Ray Photoelectron Spectroscopy (XPS) of samples was performed using a Thermo Fisher Scientific Nexsa spectrometer. Samples were analysed using a micro-focused monochromatic Al X-ray source (72 W) over an area of approximately 400 mm. Data were recorded at pass energies of 150 eV for survey scans and 40 eV for high resolution scan with 1 eV and 0.1 eV step sizes respectively. Charge neutralisation was achieved using a combination of low energy electrons and argon ions. The resulting spectra were analysed using Casa XPS peak fitting software and sample charging corrected using the C 1s signal at 284.8 eV as reference.
The morphology of the catalysts was characterised by scanning electron microscopy (SEM) on a scanning electron microscope (SEM, JEOL 840F).
High-resolution transmission electron microscopy (HRTEM) images were obtained in a probe corrected JEOL ARM200F operated at 200 kV with a Gatan GIF Quantum 965 ER spectrometer.
The conversion of CO2 and H2 with the Fe—Mn—K (10:1:1) catalyst prepared with citric acid as described above in illustrated in
The GC-MS spectrum of collected liquid products from the CO2 hydrogenation is presented in
The powder X-ray diffraction (XRD) spectrum of above catalyst precursor, activated catalyst and the used catalyst is presented in
The surface elemental compositions and oxidation states of the metals were analysed by using XPS in the region of 0-1350 eV. The survey spectrum (
The scanning electron microscopy (SEM) images of the catalyst and used catalysts were shown in
The high-resolution transmission electron microscopy (HRTEM) of the catalyst precursor and used catalyst is shown in
Catalysts of Fe—Zn—K and Fe—Cu—K were prepared with the same method as catalyst Fe—Mn—K. The catalytic performances of CO2 hydrogenation on different catalysts were shown in Table 23. The molar ratio of K and Mn(Zn or Cu) to Fe was 1:10, data were obtained at the reaction time of 20 hours.
The different base metals were also applied as promoters on the catalysts for the CO2 hydrogenation, the catalytic performances are listed in Table 24. The molar ratio of base metal and Mn to Fe was 1:10, and data was obtained at the reaction time of 20 hours
It can be seen from Table 24, the Na, K, and Cs have shown both high activities on CO2 hydrogenation and high selectivity on jet fuel range, The Fe—Mn—K catalyst showed slightly better performance on CO2 conversion and target product selectivity compared with the catalysts of Fe—Mn—Na and Fe—Mn—Cs.
A series of catalysts of Fe—Mn—K (molar ratio 10:1:1) have been prepared with different organic compounds applied in catalysts preparation, their catalytic performance on CO2 hydrogenation are presented in Table 25.
It is clear that, compared with the catalyst prepared without organic compound, all the Fe—Mn—K catalysts prepared with organic compounds showed both higher CO2 conversion and higher jet fuel range hydrocarbons selectivity, the catalysts prepared with EDTA, citric acid, oxalic acid, NTA, DTPA, Tartaric acid, HEDTA, and salicylic acid showed better catalytic performance.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference in their entirety and to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein (to the maximum extent permitted by law).
All headings and sub-headings are used herein for convenience only and should not be construed as limiting the invention in any way.
The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise paragraphed. No language in the specification should be construed as indicating any non-paragraphed element as essential to the practice of the invention.
The citation and incorporation of patent documents herein is done for convenience only and does not reflect any view of the validity, patentability, and/or enforceability of such patent documents.
This invention includes all modifications and equivalents of the subject matter recited in the paragraphs appended hereto as permitted by applicable law.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1904620.0 | Apr 2019 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/GB2020/050869 | 4/1/2020 | WO | 00 |
