WO2012031330A1 - Catalyst and method for producing same - Google Patents

Catalyst and method for producing same Download PDF

Info

Publication number
WO2012031330A1
WO2012031330A1 PCT/AU2011/001162 AU2011001162W WO2012031330A1 WO 2012031330 A1 WO2012031330 A1 WO 2012031330A1 AU 2011001162 W AU2011001162 W AU 2011001162W WO 2012031330 A1 WO2012031330 A1 WO 2012031330A1
Authority
WO
WIPO (PCT)
Prior art keywords
transition metal
catalyst
sulfide
nanoparticles
composite
Prior art date
Application number
PCT/AU2011/001162
Other languages
French (fr)
Inventor
Gao Qing Lu
Ronggang Ding
Original Assignee
The University Of Queensland
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 The University Of Queensland filed Critical The University Of Queensland
Publication of WO2012031330A1 publication Critical patent/WO2012031330A1/en

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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B01J35/19—
    • B01J35/23—
    • B01J35/30—
    • B01J35/60—
    • B01J35/612—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis

Definitions

  • the present invention relates to a method of making a catalyst comprising a composite of transition metal containing nanoparticles in a silicate framework.
  • the present invention further relates to a catalyst comprising a composite of transition metal containing nanoparticles in a silicate framework.
  • the present invention also relates to a method of conducting a chemical reaction using the catalyst of the invention.
  • transition metal containing nanoparticles means nanoparticles comprising one or more transition metals each in the form of an element or a compound.
  • a major challenge in the commercial application of certain catalysed chemical reactions is the high cost of and/or complex synthesis routes required for many catalysts.
  • An important example of such a chemical reaction is the production of alcohols from syngas (H 2 and CO) which employs the use of a variety of catalysts. Many of those catalysts are based on expensive transition metals, such as rhodium. Alcohols, and particularly ethanol, are being considered as potential alternative synthetic fuels for automobiles and there is accordingly much interest in developing cost-effective processes for their production.
  • the process to deposit the Ni-MoS 2 generally involves a number of sequential process steps for applying the catalytic materials to the silicate support and often results in the catalytic materials being deposited within the pore structure of the silicate support and in accessible to the syngas. It is accordingly an object of the present invention to provide a catalyst and method for its manufacture which overcomes or at least alleviates one or more of the disadvantages of the prior art.
  • a method of producing a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework including the steps of: providing an aqueous suspension of an exfoliated silicate, providing a solution of a first transition metal sulfide, providing a solution of a second transition metal salt, mixing together the aqueous suspension of exfoliated silicate and the transition metal containing solutions, causing precipitation of a composite precursor, separating the composite precursor, and calcining the composite precursor to form a catalyst comprising a composite of first and second transition metal containing nanoparticles in an exfoliated silicate framework, said nanoparticles including first and second transition metal sulfides.
  • the first transition metal may be molybdenum.
  • the second transition metal may be nickel, cobalt or iron.
  • the method of the present invention therefore enables the production of a composite product by forming a product precursor in a single stage, using a so-called "one-pot" synthesis approach.
  • the product precursor is formed by adding together the silicate suspension and the two or more transition metal solutions in a single stage to form a precipitate including the first transition metal and the second transition metal onto the exfoliated silicate. This thereby greatly simplifies the overall process for synthesis of the composite.
  • This aspect of the invention is a significant improvement over some prior art synthesis routes, particularly those involving impregnation of a metal into a supporting framework which may require multiple impregnation and drying and/or calcining stages
  • the exfoliated silicate may be an exfoliated layered clay.
  • the layered clay may comprise one or more of laponite, montmorillonite, bentonite, hectorite, and beidellite.
  • the exfoliated clay suspension may be made by mixing the layered clay in water .
  • the aqueous suspension of the silicate may also contain an exfoliating agent.
  • the exfoliating agent may be a surfactant.
  • the surfactant may be a non-ionic surfactant, such as a polyethylene oxide (PEO) surfactant.
  • From 2 to 20g of the surfactant may be added per 200 ml of the aqueous suspension of silicate.
  • the solution of the first transition metal sulfide may be formed by reaction of a first transition metal precursor and a sulfide precursor.
  • the first transition metal sulfide is MoS 2
  • the first transition metal precursor may comprise
  • the reaction of the first transition metal precursor and the sulfide precursor may occur prior to or during the mixing step.
  • the second transition metal salt may comprise a sulfide, halide, nitrate, acetate, oxalate, carbonate, or sulfate.
  • suitable first and second transition metal salts include (NH 4 ) 2 lv1oS 4 and nickel acetate, respectively.
  • Precipitation of the composite precursor is generally effected by conducting the precipitation step under autogeneous conditions. This may require subjecting the reaction products from mixing the transition metal solutions and silicate suspension to an ageing step.
  • the ageing may be conducted at an elevated temperature, preferably greater than 90°C, more preferably greater than 100°C, such as about 130°C or higher.
  • the aging may preferably be performed under autogenous conditions, such as in an autoclave.
  • the composite precursor may be at least partially precipitated in the mixing step.
  • the composite precursor comprises a material comprising the first and second transition metals and the exfoliated silicate that is able to be converted to the composite upon calcination.
  • the calcining step may be conducted under a non oxidising atmosphere.
  • the non oxidising atmosphere may comprise nitrogen, argon or helium.
  • the method may include additional process steps.
  • the method may include a step of drying the precipitate after the separating step.
  • the present invention also provides a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework produced according to the method of the invention.
  • the present invention also provides a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework, wherein the transition metal nanoparticles include one or more transition metal sulfides.
  • the nanoparticles comprise sulfides of the first and second transition metals.
  • the first and second transition metal sulfides may comprise separate phases or components of a single phase.
  • the first transition metal sulfide in the nanoparticles may be doped or undoped. Where the first transition metal sulfide is MoS 2 , it may be doped with an alkali dopant.
  • the alkali dopant may comprise one or more of potassium, strontium, barium, lanthanum, sodium or cesium. In an embodiment, the alkali dopant is potassium.
  • the second transition metal sulfide may comprise NiS 2 , CoS 2 or FeS 2 .
  • the catalyst may additionally include a promoter.
  • the promoter may comprise one or more of rhodium, ruthenium, plutonium or palladium.
  • the promoter may be introduced during formation of the catalyst precursor.
  • the promoter may be present in a small quantity. For example the ratio of promoter to catalyst may be from 1 :50 to 1 : 100.
  • the dopant and/or promoter have been found to promote the catalytic activity of the catalyst when used in reactions for conversion of syngas and their function is to shift the reaction products from hydrocarbons to alcohols.
  • the nanoparticles may have a particle size of less than 50 nm. In an embodiment the particle size of the nanoparticles is less than 20 nm. The particle size may be less than 15 nm.
  • the nanoparticles may have an active surface area of at least 2 m 2 /g, such as at least 2.5 m 2 /g. In an embodiment the nanoparticles have a surface area of 3 m 2 /g or higher.
  • the transition metal sulfides comprise molybdenum sulfide and nickel sulfide. In another embodiment, the transition metal sulfides comprise molybdenum sulfide and cobalt sulfide. Without wishing to be bound by theory, it is believed that the at least two transition metal sulfides exist as two discrete phases in close association with each other within the silicate framework. This close contact significantly enhances the synergetic effect between these two phases and creates favorable active sites for catalysis of chemical reactions.
  • the sulfide particles may have a particle size of less than 50 nm. In an embodiment, the particle size may be less than 20 nm. Sintering of the nanoparticles can be avoided under the high temperature conditions of calcination of the catalyst and catalysis reactions by the silicate framework acting as the structural scaffold.
  • the present invention also provides a catalyst including a composite comprising transition metal containing nanoparticles in a silicate framework as described above.
  • the present invention also provides a method of conducting a chemical reaction which is catalysed using the catalyst of the present invention.
  • the catalysed chemical reaction produces an oxygenated product from H 2 and CO (syngas).
  • the oxygenated product may be an alcohol, particularly ethanol or a higher carbon alcohol.
  • the catalyst of the present invention is also useful in the catalysation of other reactions.
  • the catalyst may be used for hydrodesulfurisation or hydrodenitrogenation reactions. These reactions are catalytic chemical processes widely used to remove sulfur and nitrogen, respectively, from natural gas and refined petroleum products primarily for the purposes of emissions control.
  • Figure 1 (a) and (b) shows TEM images of CoMoS x and NiMoS x catalysts, respectively, manufactured according to the one pot method of the present invention.
  • Figure 2(a) and (b) shows TEM images of CoMoS x and NiMoS x catalysts, respectively, manufactured according to an impregnation process of the prior art.
  • Example 1
  • the catalysts were used to catalyse production of alcohol from syngas.
  • the reaction was conducted at 300°C and up to 5 MPa in a vertical steel tube reactor.
  • the results are presented in Table 1 , together with comparative performance data for other types of catalysts.
  • X co CO conversion; HC: total hydrocarbons including methane; C r OH: methanol; C 2 -OH: ethanol; C 3+ -OH: all the alcohol products except methanol and ethanol; N/A data not available or applicable.
  • Carbon selectivity is defined as the selectivity of all the carbon-containing products formed from converted carbon, and the values are recalculated from the original reported data
  • Table 1 shows the comparison of the inventive catalyst (AIBN-NiMoS 2 ) with rhodium based catalysts and other MoS 2 based catalysts. The results indicate that the inventive catalyst exhibited reasonably good selectivity to C 2+ alcohol and significantly lower selectivity to undesirable hydrocarbon at medium operating conditions.
  • the selectivity to ethanol on Rh-based catalysts ranged from 29 to 50 % while the inventive catalyst demonstrated a selectivity to ethanol of 37%.
  • the inventive catalyst demonstrated a selectivity to ethanol of 37%.
  • the higher CO conversion on 6Rh1 .5Mn/Si0 2 can be greatly ascribed to the use of microchannel reactor, which also emphasizes the importance of reactor design and micro-scale engineering of the catalyst support to enhance the mass and heat transfer.
  • the catalyst of the invention was used to catalyse the production of ethanol from syngas.
  • the catalyst successfully shifted the Fischer-Tropsch pathway towards the alcohol synthesis route.
  • Selectivity of 87% to alcohols was produced on the studied NiMoS 2 /clay catalyst with 53.7% of C 2+ alcohols (C0 2 -free basis).
  • the data showed that the CH X hydrogenation has been successfully suppressed over the catalyst.
  • the data comparison also indicated that NiMoS 2 /clay catalyst with smaller particle size exhibits better selectivity towards the formation of ethanol. It is also interesting to note that the selectivity gain for methanol is much smaller than that for ethanol on the NiMoS 2 /clay catalyst at elevated pressure.
  • NiMoS 2 and CoMoS 2 catalyst nanocomposites were synthesised using different methods. Each catalyst composition was synthesized by the so called one-pot method of the invention and by the traditional impregnation method of the prior art. Chemisorption measurements of H 2 were carried out on an Autosorb-1 analyzer. The metal surface area (Sm, in m2/g) and metal particle size (d, in nm) were determined from the H 2 chemisorption data. The results are presented in Table 2. (I denotes impregnation method and O denotes one-pot method of the invention).
  • Figure 1 shows the TEM images of CoMoS 2 -0 and NiMoS 2 -0 catalysts produced according to the invention.
  • the NiMoS 2 and CoMoS 2 particles have the size range of 6-1 1 nm and 7-15 nm, respectively, which is close to the average particle size of 7.9 nm and 9.8 nm, respectively, from the H 2 chemisorption data.
  • Figure 1 (a) and (b) that the microstructure of the inventive composites showed CoS x and NiS x metal crystallites, respectively, anchored on the edges of MoS x . This close contact significantly enhanced the synergetic effect between these two phases and created favorable active sites for dissociation of CO and H 2 and eventual transformation into desirable alcohol products.
  • sintering of the restricted nanosized particles can be avoided under the operating conditions with by silicate framework acting as the structural scaffold.
  • Figure 2 shows the NiMoS x and CoMoS x particles having a particle size range of 9-15 nm and 9-17 nm, respectively, close to the average particle size of 1 1 nm and 12.1 nm, respectively, from the H 2 chemisorption results in Table 2.
  • the reduced particle sizes and increased active surface areas using the method of the invention indicated that more activated metal surfaces are exposed with smaller particles produced as compared with the impregnation process of the prior art.
  • the catalytic reaction was conducted on a fixed-bed reactor at 3-5 MPa and 300 °C.
  • the promoters were added to the composite before reaction. The results are shown in Table 3.
  • NiMoS2-l 5.0 4.0 24.9 22.5 43.2 23.1 7.5 1.3

Abstract

A method of producing a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework including the steps of: providing an aqueous suspension of an exfoliated silicate, providing a solution of first transition metal sulfide, providing a solution of a second transition metal salt, mixing together the aqueous suspension of exfoliated silicate and the transition metal containing solutions, causing precipitation of a composite precursor, separating the composite precursor, and calcining the composite precursor to form a catalyst comprising a composite of first and second transition metal containing nanoparticles in an exfoliated silicate framework, said nanoparticles including sulfides of the first and second transition metals.

Description

CATALYST AND METHOD FOR PRODUCING SAME
Field of the invention
The present invention relates to a method of making a catalyst comprising a composite of transition metal containing nanoparticles in a silicate framework. The present invention further relates to a catalyst comprising a composite of transition metal containing nanoparticles in a silicate framework. The present invention also relates to a method of conducting a chemical reaction using the catalyst of the invention.
Background to the invention As used herein the term "transition metal containing nanoparticles" means nanoparticles comprising one or more transition metals each in the form of an element or a compound.
A major challenge in the commercial application of certain catalysed chemical reactions is the high cost of and/or complex synthesis routes required for many catalysts. An important example of such a chemical reaction is the production of alcohols from syngas (H2 and CO) which employs the use of a variety of catalysts. Many of those catalysts are based on expensive transition metals, such as rhodium. Alcohols, and particularly ethanol, are being considered as potential alternative synthetic fuels for automobiles and there is accordingly much interest in developing cost-effective processes for their production.
Many researchers have been investigating the replacement of expensive existing catalysts, such as rhodium based catalysts, with more cost effective catalyst systems, such as those based on less expensive materials like molybdenum sulfide. However the alternative catalysts developed to date suffer from the disadvantages of poor or inconsistent performance and/or complex multi-stage synthesis routes. One such system involves the use of an Ni-MoS2 catalyst on a support, typically a silicate support. The production of these catalysts systems is complex and can give rise to inefficient use of the Ni-MoS2. The process to deposit the Ni-MoS2 generally involves a number of sequential process steps for applying the catalytic materials to the silicate support and often results in the catalytic materials being deposited within the pore structure of the silicate support and in accessible to the syngas. It is accordingly an object of the present invention to provide a catalyst and method for its manufacture which overcomes or at least alleviates one or more of the disadvantages of the prior art.
Description of the invention According to the present invention there is provided a method of producing a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework including the steps of: providing an aqueous suspension of an exfoliated silicate, providing a solution of a first transition metal sulfide, providing a solution of a second transition metal salt, mixing together the aqueous suspension of exfoliated silicate and the transition metal containing solutions, causing precipitation of a composite precursor, separating the composite precursor, and calcining the composite precursor to form a catalyst comprising a composite of first and second transition metal containing nanoparticles in an exfoliated silicate framework, said nanoparticles including first and second transition metal sulfides.
The first transition metal may be molybdenum.
The second transition metal may be nickel, cobalt or iron. The method of the present invention therefore enables the production of a composite product by forming a product precursor in a single stage, using a so-called "one-pot" synthesis approach. The product precursor is formed by adding together the silicate suspension and the two or more transition metal solutions in a single stage to form a precipitate including the first transition metal and the second transition metal onto the exfoliated silicate. This thereby greatly simplifies the overall process for synthesis of the composite. This aspect of the invention is a significant improvement over some prior art synthesis routes, particularly those involving impregnation of a metal into a supporting framework which may require multiple impregnation and drying and/or calcining stages
Further, by virtue of the method of the present invention, the first transition metal sulfide and the second transition metal are precipitated in situ onto the exfoliated silicate. This favours formation of a composite having highly dispersed nanoparticles of reduced particle size, increased active surface area and greater homogeneous distribution as compared with prior art catalysts. The catalysts of the present invention thereby have improved synergy between the nanoparticles and framework and exhibit enhanced catalytic activity over many prior art catalysts. The exfoliated silicate may be an exfoliated layered clay. The layered clay may comprise one or more of laponite, montmorillonite, bentonite, hectorite, and beidellite. The exfoliated clay suspension may be made by mixing the layered clay in water . The aqueous suspension of the silicate may also contain an exfoliating agent. The exfoliating agent may be a surfactant. The surfactant may be a non-ionic surfactant, such as a polyethylene oxide (PEO) surfactant.
From 2 to 20g of the surfactant may be added per 200 ml of the aqueous suspension of silicate.
The solution of the first transition metal sulfide may be formed by reaction of a first transition metal precursor and a sulfide precursor. Where the first transition metal sulfide is MoS2, the first transition metal precursor may comprise
Figure imgf000005_0001
and the sulfide precursor may comprise (NH4)2S. The reaction of the first transition metal precursor and the sulfide precursor may occur prior to or during the mixing step.
The second transition metal salt may comprise a sulfide, halide, nitrate, acetate, oxalate, carbonate, or sulfate. Examples of suitable first and second transition metal salts include (NH4)2lv1oS4 and nickel acetate, respectively.
Precipitation of the composite precursor is generally effected by conducting the precipitation step under autogeneous conditions. This may require subjecting the reaction products from mixing the transition metal solutions and silicate suspension to an ageing step. The ageing may be conducted at an elevated temperature, preferably greater than 90°C, more preferably greater than 100°C, such as about 130°C or higher. The aging may preferably be performed under autogenous conditions, such as in an autoclave.
The composite precursor may be at least partially precipitated in the mixing step. The composite precursor comprises a material comprising the first and second transition metals and the exfoliated silicate that is able to be converted to the composite upon calcination.
The calcining step may be conducted under a non oxidising atmosphere. The non oxidising atmosphere may comprise nitrogen, argon or helium. The method may include additional process steps. For example the method may include a step of drying the precipitate after the separating step.
The present invention also provides a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework produced according to the method of the invention. The present invention also provides a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework, wherein the transition metal nanoparticles include one or more transition metal sulfides.
In an embodiment, the nanoparticles comprise sulfides of the first and second transition metals. The first and second transition metal sulfides may comprise separate phases or components of a single phase.
The first transition metal sulfide in the nanoparticles may be doped or undoped. Where the first transition metal sulfide is MoS2, it may be doped with an alkali dopant. The alkali dopant may comprise one or more of potassium, strontium, barium, lanthanum, sodium or cesium. In an embodiment, the alkali dopant is potassium.
The second transition metal sulfide may comprise NiS2, CoS2 or FeS2.
The catalyst may additionally include a promoter. The promoter may comprise one or more of rhodium, ruthenium, plutonium or palladium. The promoter may be introduced during formation of the catalyst precursor. The promoter may be present in a small quantity. For example the ratio of promoter to catalyst may be from 1 :50 to 1 : 100.
The dopant and/or promoter have been found to promote the catalytic activity of the catalyst when used in reactions for conversion of syngas and their function is to shift the reaction products from hydrocarbons to alcohols.
The nanoparticles may have a particle size of less than 50 nm. In an embodiment the particle size of the nanoparticles is less than 20 nm. The particle size may be less than 15 nm. The nanoparticles may have an active surface area of at least 2 m2/g, such as at least 2.5 m2/g. In an embodiment the nanoparticles have a surface area of 3 m2/g or higher.
In one embodiment the transition metal sulfides comprise molybdenum sulfide and nickel sulfide. In another embodiment, the transition metal sulfides comprise molybdenum sulfide and cobalt sulfide. Without wishing to be bound by theory, it is believed that the at least two transition metal sulfides exist as two discrete phases in close association with each other within the silicate framework. This close contact significantly enhances the synergetic effect between these two phases and creates favorable active sites for catalysis of chemical reactions. The sulfide particles may have a particle size of less than 50 nm. In an embodiment, the particle size may be less than 20 nm. Sintering of the nanoparticles can be avoided under the high temperature conditions of calcination of the catalyst and catalysis reactions by the silicate framework acting as the structural scaffold.
The present invention also provides a catalyst including a composite comprising transition metal containing nanoparticles in a silicate framework as described above.
The present invention also provides a method of conducting a chemical reaction which is catalysed using the catalyst of the present invention.
In an embodiment, the catalysed chemical reaction produces an oxygenated product from H2 and CO (syngas). The oxygenated product may be an alcohol, particularly ethanol or a higher carbon alcohol. We have found that the catalyst of the present invention is also useful in the catalysation of other reactions. In another embodiment the catalyst may be used for hydrodesulfurisation or hydrodenitrogenation reactions. These reactions are catalytic chemical processes widely used to remove sulfur and nitrogen, respectively, from natural gas and refined petroleum products primarily for the purposes of emissions control.
Brief description of the drawings
The invention will be better understood by reference to the following examples and accompanying drawings, in which:
Figure 1 (a) and (b) shows TEM images of CoMoSx and NiMoSx catalysts, respectively, manufactured according to the one pot method of the present invention.
Figure 2(a) and (b) shows TEM images of CoMoSx and NiMoSx catalysts, respectively, manufactured according to an impregnation process of the prior art. Example 1
(ΝΗ4)6Μθ7θ244Η20 solution and (NH4)2S solution were mixed to give a solution of (NH4)2MoS4. Nickel nitrate solution and (NH4)2MoS4 solution were added dropwise into a clay suspension containing polyethylene oxide surfactant. The resulting black slurry was transferred into an autoclave and kept at 130°C for 24 hrs. The precipitate was recovered from the mixture by filtering and washing with distilled water. The precipitate was dried, calcined and ground with an alkaline promoter comprising K2C03 for the catalytic reaction. The produced catalysts were characterized by N2 adsorption, SEM, TEM and
H2-chemisorption.
The catalysts were used to catalyse production of alcohol from syngas. The reaction was conducted at 300°C and up to 5 MPa in a vertical steel tube reactor. The results are presented in Table 1 , together with comparative performance data for other types of catalysts.
The comparison of testing results on AIBN-NiMoS2 catalyst
with literature data
Experimental conditions Carbon selectivity(%)
Catalyst T P GHSV H2/CO HC CrOH C2-OH C3+-OH
(°C) (MPa) in"1) (%)
NiMoS2(Dow) 295 10.45 1300 1.0 29.2 14.5 22.7 40.7 17.4
K2CO3C0M0S2 270 14.3 2546 1.1 10.4 12.7 48.2 29.6 7.8
AIBN-NiMoS2 300 5 2100 2.0 4.9 13 40.2 37.0 9.7
2Rh4.5Ce/Si02 350 0.1 300 1.7 NA 50.9 3.0 45.0 N/A
1RhO.5SmO.5V/SiO 280 3 13000 2.0 4.9 35.5 10.5 29.5 1.7
2
1Rh/Zr02 220 0.1 NA 1.0 2.0 31.5 15.4 50.8 N/A
1RWV205 220 0.1 NA 1.0 4.5 50.5 6.2 37.2 N/A
2Rh10Fe/AI2O3 270 1 NA 1.0 3.8 29 12 50 N/A
1.2Rh1.2Mn0.09LiO 330 3 12000 2.0 8.3 27.3 1.1 31.4 N/A
.06Fe in CNT
*6Rh1.5Mn/Si02 300 5.3 3750 2.0 40.5 50.5 3.5 45 2 lest on a microchannel reactor while other used a fixed-bed reactor.
Xco: CO conversion; HC: total hydrocarbons including methane; CrOH: methanol; C2-OH: ethanol; C3+-OH: all the alcohol products except methanol and ethanol; N/A data not available or applicable. Carbon selectivity is defined as the selectivity of all the carbon-containing products formed from converted carbon, and the values are recalculated from the original reported data Table 1 shows the comparison of the inventive catalyst (AIBN-NiMoS2) with rhodium based catalysts and other MoS2 based catalysts. The results indicate that the inventive catalyst exhibited reasonably good selectivity to C2+ alcohol and significantly lower selectivity to undesirable hydrocarbon at medium operating conditions. The selectivity to ethanol on Rh-based catalysts ranged from 29 to 50 % while the inventive catalyst demonstrated a selectivity to ethanol of 37%. With a low CO conversion below 8.3% for Rh catalyst group and AIBN-MoS2 catalyst, the latter exhibited a significantly lower selectivity to undesirable hydrocarbon. The higher CO conversion on 6Rh1 .5Mn/Si02 can be greatly ascribed to the use of microchannel reactor, which also emphasizes the importance of reactor design and micro-scale engineering of the catalyst support to enhance the mass and heat transfer.
The comparison with other MoS2-based catalysts showed that the inventive catalyst exhibited comparable performance with Dow NiMoS2 catalyst. However, it should be recognized that the Dow catalyst was tested under a much higher pressure of 10.45 MPa, at which thermodynamics would predict maximized CO conversion and ethanol selectivity. In terms of the ethanol selectivity, the inventive catalyst exceeded the performance of all the other MoS2-based catalysts (excluding the Dow catalyst) despite those other catalysts operating at higher pressures (ranging from 7.9-14.3 MPa).
The catalyst of the invention was used to catalyse the production of ethanol from syngas. The catalyst successfully shifted the Fischer-Tropsch pathway towards the alcohol synthesis route. Selectivity of 87% to alcohols was produced on the studied NiMoS2/clay catalyst with 53.7% of C2+alcohols (C02-free basis). The data showed that the CHX hydrogenation has been successfully suppressed over the catalyst. The data comparison also indicated that NiMoS2/clay catalyst with smaller particle size exhibits better selectivity towards the formation of ethanol. It is also interesting to note that the selectivity gain for methanol is much smaller than that for ethanol on the NiMoS2/clay catalyst at elevated pressure. This implies that high pressure favors the formation of ethanol and higher selectivity to ethanol is expected under higher reaction pressures. This result verified a recent study showing that elevated pressure increases the equilibrium concentration of ethanol from the hydrogenation of CO. Accordingly, this Example shows that highly dispersed multi-transition metal nanoparticles have been produced within a silicate framework and that better synergetic confinement among the metal nanoparticles and framework is achieved. It is suggested that the nanosized metal particles enhanced the activity towards the formation of alcohol.
Example 2
NiMoS2 and CoMoS2 catalyst nanocomposites were synthesised using different methods. Each catalyst composition was synthesized by the so called one-pot method of the invention and by the traditional impregnation method of the prior art. Chemisorption measurements of H2 were carried out on an Autosorb-1 analyzer. The metal surface area (Sm, in m2/g) and metal particle size (d, in nm) were determined from the H2 chemisorption data. The results are presented in Table 2. (I denotes impregnation method and O denotes one-pot method of the invention).
Table 2: H2 Chemisorption Data
Sample uptake (pmol/g) Particle siz Active
(nm) Surface area
(m2/g)
NiMoS2-l 39 1 1 3.1
NiMoS2-0 54 7.9 4.2 CoMoS2-l 35 12.1 2.9
CoMoS2- 43 9.8 3.4 O
Figure 1 shows the TEM images of CoMoS2-0 and NiMoS2-0 catalysts produced according to the invention. The NiMoS2 and CoMoS2 particles have the size range of 6-1 1 nm and 7-15 nm, respectively, which is close to the average particle size of 7.9 nm and 9.8 nm, respectively, from the H2 chemisorption data. It can be seen from Figure 1 (a) and (b) that the microstructure of the inventive composites showed CoSx and NiSx metal crystallites, respectively, anchored on the edges of MoSx. This close contact significantly enhanced the synergetic effect between these two phases and created favorable active sites for dissociation of CO and H2 and eventual transformation into desirable alcohol products. On the other hand, sintering of the restricted nanosized particles can be avoided under the operating conditions with by silicate framework acting as the structural scaffold.
Figure 2 shows the NiMoSx and CoMoSx particles having a particle size range of 9-15 nm and 9-17 nm, respectively, close to the average particle size of 1 1 nm and 12.1 nm, respectively, from the H2 chemisorption results in Table 2.
The reduced particle sizes and increased active surface areas using the method of the invention indicated that more activated metal surfaces are exposed with smaller particles produced as compared with the impregnation process of the prior art.
The catalytic reaction was conducted on a fixed-bed reactor at 3-5 MPa and 300 °C. The promoters were added to the composite before reaction. The results are shown in Table 3.
Table 3: Product distribution on NiMoS2 and CoMoS2 catalysts
Catalyst P CO Selectivity (C%) (C02 free)
(MPa) Con.(%) HC CH4 MeOH EtOH PrOH Other oxy
NiMoS2-0 4.0 3.2 29.1 21.9 37.1 24.9 7.7 1.2
5.0 4.9 13.0 10.6 40.2 37.0 8.6 1.1
NiMoS2-l 5.0 4.0 24.9 22.5 43.2 23.1 7.5 1.3
CoMoS2-0 4.0 1.5 13.9 10.2 52.6 20.4 11.0 2.1
5.0 4.0 3.3 2.5 70.5 20.6 4.3 1.3
CoMoS2-l 5.0 5.7 28 25.3 51.6 15.4 3.8 1.2
Selectivity of 87% to alcohols was produced on NiMoS2-0 catalyst with 53.7% of C2+ alcohol. Extremely high selectivity of 96.7% to alcohols was achieved on CoMoS2-0 catalyst, however, methanol nominated the product distribution. The data showed that the CHx hydrogenation has been successfully suppressed over the two catalysts. The data comparison also indicated that nickel catalyst with smaller particle size exhibited better selectivity towards the formation of ethanol than cobalt catalyst. The test results suggest that the control of the size of the metal particles is crucial towards the formation of the desired product.
References to prior art in this specification are provided for illustrative purposes only are not to be taken as an admission that such prior art is part of the common general knowledge in Australia or elsewhere.
Throughout this specification and claims which follow, unless the context requires otherwise, the word "comprise" and variations such as "comprises" or "comprising" will be understood to imply the inclusion of a stated integer or group of integers or steps but not the exclusion of any other integer or group of integers or steps.
The invention described herein is susceptible to variations, modifications and/or additions other than those specifically described and it is to be understood that the invention includes all such variations modifications and/or additions which fall within the spirit and scope of the above description.

Claims

1 . A method of producing a catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework including the steps of: providing an aqueous suspension of an exfoliated silicate, providing a solution of first transition metal sulfide, providing a solution of a second transition metal salt, mixing together the aqueous suspension of exfoliated silicate and the transition metal containing solutions, causing precipitation of a composite precursor, separating the composite precursor, and calcining the composite precursor to form a catalyst comprising a composite of first and second transition metal containing nanoparticles in an exfoliated silicate framework, said nanoparticles including sulfides of the first and second transition metals.
2. The method of claim 1 , wherein the first transition metal is molybdenum.
3. The method of claim 1 , wherein the second transition metal is one or more of nickel, cobalt and iron.
4. The method of claim 1 , wherein the exfoliated silicate is an exfoliated layered clay.
5. The method of claim 4, wherein layered clay comprises one or more of laponite, montmorillonite, bentonite, hectorite, and beidellite.
6. The method of claim 1 , wherein the aqueous suspension of an exfoliated silicate is made by mixing the silicate in water.
7. The method of claim 1 , wherein the aqueous suspension of an exfoliated silicate also contains an exfoliating agent.
8. The method of claim 7, wherein the exfoliating agent is a surfactant.
9. The method of claim 8, wherein the surfactant is a non-ionic surfactant, such as a polyethylene oxide (PEO) surfactant.
10. The method of claim 8, wherein from 2 to 20g of the surfactant is added per 200 ml of the aqueous suspension of silicate.
1 1. The method of claim 1 , wherein the solution of the first transition metal sulfide is formed by reaction of a first transition metal precursor and a sulfide precursor.
12. The method of claim 2, wherein the first transition metal precursor is
Figure imgf000016_0001
and the sulfide precursor is (NH4)2S.
13. The method of claim 1 , wherein the second transition metal salt is a sulfide, halide, nitrate, acetate, oxalate, carbonate, or sulfate.
14. The method of claim 1 , wherein the first transition metal sulfide is
(NH4)2MoS4 and the second transition metal salt is nickel acetate.
15. The method of claim 1 , wherein the precipitation step is conducted under autogeneous conditions.
16. The method of claim 1 , wherein the reaction products from mixing the transition metal solutions and silicate suspension are subjected to an ageing step.
17. The method of claim 16, wherein the ageing step is conducted at an elevated temperature, preferably greater than 90°C, more preferably greater than 100°C, such as about 130°C or higher.
18. The method of claim 1 , wherein the composite precursor is at least partially precipitated in the mixing step.
19. The method of claim 1 , wherein the calcining step is conducted under a non oxidising atmosphere.
20. The method of claim 20, wherein the non oxidising atmosphere comprises nitrogen, argon or helium.
21. A catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework produced according to the process of claim 1 .
22. A catalyst comprising a composite of transition metal containing nanoparticles in an exfoliated silicate framework, wherein the transition metal nanoparticles include one or more transition metal sulfides.
23. The catalyst of claim 21 or 22, wherein the nanoparticles comprise sulfides of the first and second transition metals.
24. The catalyst of claim 23, wherein the first and second transition metal sulfides comprise separate phases or components of a single phase.
25. The catalyst of claim 23, wherein the first transition metal sulfide in the nanoparticles is doped.
26. The catalyst of claim 25, wherein the first transition metal sulphide is doped with an alkali dopant.
27. The catalyst of claim 26 wherein, the alkali dopant comprises one or more of potassium, strontium, barium, lanthanum, sodium or cesium, and is preferably potassium.
28. The catalyst of claim 21 or 22, wherein the second transition metal sulfide comprises NiS2, CoS2 or FeS2.
29. The catalyst of claim 21 or 22, additionally including a promoter.
30. The catalyst of claim 29, wherein the promoter comprises one or more of rhodium, ruthenium, plutonium or palladium.
31. The catalyst of claim 29, wherein the promoter is introduced during formation of the catalyst precursor.
32. The catalyst of claim 29, wherein the ratio of promoter to catalyst is from 1 :50 to 1 : 100.
33. The catalyst of claim 21 or 22, wherein the nanoparticles have a particle size of less than 50 nm.
34. The catalyst of claim 21 or 22, wherein the nanoparticles have an active surface area of at least 2 m2/g.
35. The catalyst of claim 21 or 22, wherein the transition metal sulfides comprise molybdenum sulfide and one of nickel sulfide and cobalt sulfide.
36. A method of conducting a chemical reaction which is catalysed using the catalyst of claim 21 or claim 22.
37. The method of claim 36, wherein the catalysed chemical reaction produces an oxygenated product from H2 and CO (syngas).
38. The method of claim 37, wherein the oxygenated product is an alcohol, particularly ethanol or a higher carbon alcohol.
PCT/AU2011/001162 2010-09-10 2011-09-09 Catalyst and method for producing same WO2012031330A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34468410P 2010-09-10 2010-09-10
US61/344,684 2010-09-10

Publications (1)

Publication Number Publication Date
WO2012031330A1 true WO2012031330A1 (en) 2012-03-15

Family

ID=45810024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2011/001162 WO2012031330A1 (en) 2010-09-10 2011-09-09 Catalyst and method for producing same

Country Status (1)

Country Link
WO (1) WO2012031330A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104399494A (en) * 2014-12-10 2015-03-11 吉林大学 Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production
US20150129463A1 (en) * 2013-11-09 2015-05-14 Research Institute Of Petroleum Industry (Ripi) Nanocatalyst for heavy crude oil upgrading and method for synthesizing same
WO2016065253A1 (en) * 2014-10-23 2016-04-28 Leal Juan Synthesis of molybdenum sulfide (mos2) and tungsten sulfide (ws2) catalyst
WO2016126550A1 (en) * 2015-02-02 2016-08-11 Novinda Corporation Expanded, mercury-sorbent materials
CN107799769A (en) * 2017-02-20 2018-03-13 湖南大学 A kind of nanometer curing nickel material and its preparation method and application
CN115041195A (en) * 2022-07-27 2022-09-13 广西民族大学 Composite catalyst for flue gas treatment and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169348B2 (en) * 2001-07-06 2007-01-30 University Of Queensland Method of making metal oxide nanoparticles in an exfoliated silicate framework
WO2009073785A1 (en) * 2007-12-04 2009-06-11 Albemarle Netherlands, B.V. Bulk catalyst composition comprising bulk metal oxide particles
EP2103347A1 (en) * 2008-03-17 2009-09-23 ExxonMobil Research and Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7169348B2 (en) * 2001-07-06 2007-01-30 University Of Queensland Method of making metal oxide nanoparticles in an exfoliated silicate framework
WO2009073785A1 (en) * 2007-12-04 2009-06-11 Albemarle Netherlands, B.V. Bulk catalyst composition comprising bulk metal oxide particles
EP2103347A1 (en) * 2008-03-17 2009-09-23 ExxonMobil Research and Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150129463A1 (en) * 2013-11-09 2015-05-14 Research Institute Of Petroleum Industry (Ripi) Nanocatalyst for heavy crude oil upgrading and method for synthesizing same
US9878319B2 (en) * 2013-11-09 2018-01-30 Research Institute Of Petroleum Industry (Ripi) Nanocatalyst for heavy crude oil upgrading and method for synthesizing same
WO2016065253A1 (en) * 2014-10-23 2016-04-28 Leal Juan Synthesis of molybdenum sulfide (mos2) and tungsten sulfide (ws2) catalyst
CN104399494A (en) * 2014-12-10 2015-03-11 吉林大学 Carbon-coated cobalt sulfide material as well as preparing method thereof and application of carbon-coated cobalt sulfide material in aspect of water cracking hydrogen production
CN104399494B (en) * 2014-12-10 2016-04-20 吉林大学 The coated cobalt sulfide material of a kind of carbon, preparation method and the application in water-splitting product hydrogen thereof
WO2016126550A1 (en) * 2015-02-02 2016-08-11 Novinda Corporation Expanded, mercury-sorbent materials
CN107799769A (en) * 2017-02-20 2018-03-13 湖南大学 A kind of nanometer curing nickel material and its preparation method and application
CN107799769B (en) * 2017-02-20 2019-11-15 湖南大学 A kind of nanometer of curing nickel material and its preparation method and application
CN115041195A (en) * 2022-07-27 2022-09-13 广西民族大学 Composite catalyst for flue gas treatment and preparation method and application thereof
CN115041195B (en) * 2022-07-27 2023-11-14 广西民族大学 Composite catalyst for flue gas treatment and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Ye et al. Recent progress in improving the stability of copper-based catalysts for hydrogenation of carbon–oxygen bonds
Taherian et al. Facile synthesis of yttria-promoted nickel catalysts supported on MgO-MCM-41 for syngas production from greenhouse gases
Tezel et al. Hydrogen production by methane decomposition using bimetallic Ni–Fe catalysts
Luk et al. Status and prospects in higher alcohols synthesis from syngas
Zhang et al. Recent advances in understanding the key catalyst factors for Fischer-Tropsch synthesis
US7163963B2 (en) Chemically and thermally stabilized alumina for Fischer-Tropsch catalysts
EP2490989B1 (en) Production of lower olefins from synthesis gas
Yurdakul et al. Preparation of Ni-based catalysts to produce hydrogen from glycerol by steam reforming process
US8618182B2 (en) Process for synthesizing C5+ hydrocarbons in the presence of a catalyst prepared using at least one cyclic oligosaccharide
JP4747339B2 (en) Iron-based catalyst for Fischer-Tropsch synthesis reaction, method for producing the same, and method for producing hydrocarbons using the same
Zeng et al. Ni–Ce–Al composite oxide catalysts synthesized by solution combustion method: Enhanced catalytic activity for CO methanation
Tao et al. Development of platinum-based bimodal pore catalyst for CO2 reforming of CH4
US7771702B2 (en) Sulfur-tolerant catalysts and related precursors and processes
WO2012031330A1 (en) Catalyst and method for producing same
KR101829917B1 (en) Mesoporous main framework of cobalt based catalyst for Fischer-Tropsch synthesis and a preparation method thereof
Awad et al. Non-oxidative decomposition of methane/methanol mixture over mesoporous Ni-Cu/Al2O3 Co-doped catalysts
Chotirach et al. Titanium nitride promoted Ni-based SBA-15 catalyst for dry reforming of methane
WO2013150305A2 (en) Alcohol production process
Qi et al. Yttria-doped Cu/ZnO catalyst with excellent performance for CO2 hydrogenation to methanol
Zhao et al. Synergistic bimetallic Ru–Pt catalysts for the low‐temperature aqueous phase reforming of ethanol
EP2301663B1 (en) Catalyst for fischer-tropsch synthesis and method for producing hydrocarbons
Arpini et al. Tuning CO2 hydrogenation selectivity by N-doped carbon coating over nickel nanoparticles supported on SiO2
Li et al. Stabilizing Ni-Co alloy on bimodal mesoporous alumina to enhance carbon resistance for dry reforming of methane
Uttamaprakrom et al. Development of Ni–Ce/Al-MCM-41 catalysts prepared from natural kaolin for CO2 methanation
KR101847549B1 (en) Methods of manufacturing iron-base catalysts and methods of manufacturing hydrocarbons using iron-base catalysts made by the method

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11822938

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11822938

Country of ref document: EP

Kind code of ref document: A1