[go: up one dir, main page]

WO2019014712A1 - Production de diméthoxyméthane par hydrogénation directe - Google Patents

Production de diméthoxyméthane par hydrogénation directe Download PDF

Info

Publication number
WO2019014712A1
WO2019014712A1 PCT/AU2018/050746 AU2018050746W WO2019014712A1 WO 2019014712 A1 WO2019014712 A1 WO 2019014712A1 AU 2018050746 W AU2018050746 W AU 2018050746W WO 2019014712 A1 WO2019014712 A1 WO 2019014712A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
support
synthesis gas
alumina
dimethoxymethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AU2018/050746
Other languages
English (en)
Inventor
Akshat Tanksale
Fan Liang Chan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monash University
Original Assignee
Monash University
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
Priority claimed from AU2017902803A external-priority patent/AU2017902803A0/en
Application filed by Monash University filed Critical Monash University
Publication of WO2019014712A1 publication Critical patent/WO2019014712A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen

Definitions

  • the present invention relates to the production of dimethoxymethane and in particular to a method of producing dimethoxymethane in a single contact step process. Background of the invention
  • Oxymethylene Ethers are a class of second generation fuel components that can be blended with diesel in large volume fractions to reduce soot emission and to make transportation fuels more sustainable. OMEs can be produced from methanol and formaldehyde using an acid catalyst. The current industrial production method of OME (also known as Dimethoxy
  • Methane, DMM is based on a two-step process whereby methanol is first partially oxidised into formaldehyde in gas phase in a first reactor, followed by liquid phase acetalization of the as-obtained formaldehyde with methanol in a second reactor.
  • This process suffers from significant losses due to the long chain of reactions starting from natural gas to produce synthesis gas, followed by methanol synthesis and then partial oxidation of methanol into formaldehyde and then the final step of acetalization to produce OMEi .
  • a process of producing dimethoxymethane comprising the steps of: a) contacting a synthesis gas of at least CO with a mixture of methanol and a catalyst at conditions of temperature and pressure to support hydrogenation of the CO in the synthesis gas to dimethoxymethane; the catalyst comprising i. catalytic material being at least one metal selected from the group of Ni, Ru, Cu, Pt and Pd; and ii. an acidic catalyst support being at least one selected from the group of zeolites, alumina, amorphous silica-alumina and silica b) separating the dimethoxymethane from the catalyst.
  • the catalyst support further includes an acidic ion exchange resin to increase the acidity of the catalyst support.
  • the synthesis gas which contains at least CO and may also contain CO 2 is fed to a reactor with methanol and catalyst.
  • the catalyst is a bifunctional catalyst which comprises a catalytic metal which catalyses the reaction of synthesis gas and hydrogen to formaldehyde and an acidic catalyst support which catalyses the acetalization of the formaldehyde to dimethoxymethane.
  • the process of the invention is able to produce dimethoxymethane directly from synthesis gas and methanol in a single contacting step.
  • the methanol and catalyst is preferably in the form of slurry and the synthesis gas mixed with the slurry in the reactor under conditions which promote hydrogenation.
  • the ratio of CO to hydrogen in the synthesis gas is preferably in the range of 1 :1 to 1 :20 but is more preferably about 1 :2.
  • the conditions to support hydrogenation of the CO in the synthesis gas initially to dimethoxymethane is a temperature in the range of 0 - 200°C, preferably 50 - 150°C, and a pressure of 50-200bar
  • the catalyst is preferably formed by loading metal oxide catalyst onto an acidic catalyst support which may have been modified to have a size pore structure to which the metal oxide is loaded.
  • a further catalyst support such as an ion exchange resin may also be added to increase the acidity of the catalyst.
  • the metal oxide on the catalytic support is then reduced to activate the catalytic metal.
  • a process of producing oxymethylene ethers comprising the steps of: a) contacting a hydrogen gas, CO and/or CO 2 with a mixture of methanol and a catalyst at conditions of temperature and pressure to support hydrogenation of the CO and/or CO 2 gas in the synthesis gas to oxymethylene ethers; the catalyst comprising: i. catalytic material being at least one metal selected from the group of Ni,
  • the catalyst is a bifunctional catalyst that comprises a catalytic metal which catalyses the reaction of synthesis gas and hydrogen to formaldehyde and an acidic catalyst support which catalyses the acetalization of the formaldehyde to oxymethylene ethers.
  • the catalyst support further includes an acidic ion exchange resin to increase the acidity of the catalyst support.
  • the acidic cation exchange resin is an acidic sulfonic acid cation exchange resin.
  • the catalytic material is at least one metal selected from the group of Ni(0), Ru(0), Cu(0), Pt(0) and Pd(0).
  • the catalytic material is at least two metals.
  • the ratio of CO and/or CO 2 to hydrogen in the synthesis gas is from 1 :1 to 1 :20. Most preferably, the ratio is from about 1 :2.
  • the ratio of CO to hydrogen in the synthesis gas is from 1 :1 to 1 :20. More preferably, the ratio is from about 1 :2.
  • the ratio of CO 2 to hydrogen in the synthesis gas is from 1 :1 to 1 :20. More preferably, the ratio is from about 1 :2. Most preferably, the ratio is from about 1 :3.
  • the contacting step is carried out at a temperature of from about 0°C up to about 200°C.
  • the temperature is from about 20°C. More preferably, the temperature is from about 40°C. Most preferably, the temperature is from about 50°C. Alternatively, or additionally, it is preferred that the temperature is up to 190°C. More preferably, the temperature is up to 180°C. Most preferably, the temperature is up to 170°C. By way of example, in one form of the invention, the temperature is from 50 up to 150°C.
  • the contacting step is carried out at a pressure of from about 50 bar up to about 200 bar.
  • the pressure is from about 60 bar. More preferably, the pressure is from about 70 bar. Most preferably, the pressure is from about 75 bar. Alternatively, or additionally, the pressure is up to about 1 75 bar. More preferably, the pressure is up to about 150 bar. Most preferably, the pressure is up to about 125 bar.
  • the pressure is from 50 up to 200bar
  • the ratio of partial pressure of hydrogen to partial pressure of CO and/or CO 2 is from about 4:1 to about 4:3. Preferably, the ratio of partial pressure of hydrogen to partial pressure of CO and/or CO 2 is about 2:1 .
  • the oxymethylene ethers comprise, consist, or consist essentially of: OME (dimethoxy methane).
  • the oxymethylene ethers comprise, consist, or consist essentially of: OME1 (dimethoxy methane) and one or more oxymethylene ether oligomers of the form OME n , wherein n is an integer of from 2 to 5. It is preferred that n is a 2 or 3, e.g. OME 2 and OME 3 .
  • OME n refers to oxymethylene dimethyl ethers of the form CH 3 (OCH 2 )nOCH3.
  • the contacting step comprises: contacting a synthesis gas including at least: hydrogen gas, CO, and/or CO 2 with the mixture of methanol and the catalyst.
  • the methanol and catalyst are in the form of slurry and the contacting step comprises mixing the synthesis gas with the slurry in the reactor under conditions which promote hydrogenation.
  • the hydrogen gas, CO, and/or CO 2 are introduced to a reactor as synthesis gas and the methanol and catalyst is introduced to the reactor as a slurry.
  • the process produces oxymethylene ethers from synthesis gas and methanol in a single contacting step.
  • a catalyst for the production of dimethoxymethane from synthesis gas in a single contacting step comprising: at least one catalytic material selected from the group of Ni, Pt, Ru, Cu and Pd; and at least one acidic catalyst support selected from the group of zeolites, alumina, amorphous silica- alumina, silica and ion exchange resin.
  • the at least one catalytic material is at least one catalytic metal selected from the group of Ni(0), Ru(0), Cu(0), Pt(0) and Pd(0).
  • the ion exchange resin is an acidic cation exchange resin.
  • the acidic cation exchange resin is an acidic sulfonic acid cation exchange resin (e.g. Amberlyst 15 supplied by Dow Chemical).
  • At least 2 catalytic metals are used and the support is at least one of the group of zeolites, alumina, amorphous silica-alumina and silica is used in conjunction with the ion exchange resin.
  • the metal/metals may be loaded onto the zeolite, alumina, amorphous silica-alumina or silica and the ion exchange resin is used to increase the acidity of the catalyst/catalyst support.
  • Figure 1 is a schematic representation of the reaction pathway of synthesis gas to dimethoxymethane
  • Figure 2 is a graph illustrating the yield obtained from the hydrogenation of CO to dimethoxymethane with 0.5 g Ru/Ni on alumina support and 0.5 g acid catalyst/ ion exchange resin (Amberlyst supplied by Dow Chemical).
  • Figure 3 is a graph showing the yield obtained from the hydrogenation of CO to dimethoxymethane with a single bifunctional catalyst Ru/Cu on zeolite support.
  • Figure 4 is a graph showing the yield obtained from the hydrogenation of CO to dimethoxymethane with a single bifunctional catalyst Ru/Ni on a zeolite support.
  • Figure 5 is a schematic diagram of a system to produce dimethoxymethane via a single contacting step process
  • Figure 6 is a schematic representation illustrating the role of a catalyst or catalysts in the production of dimethoxy methane from hydrogenation of CO.
  • Figure 7 is a graph showing the rate of OME 1 production from hydrogenation of
  • Figure 8 is a graph showing the rate of OME n production from hydrogenation of CO 2 at temperatures (a) 100 °C (b) 125 °C (c) 150 °C (d) 175 °C.
  • Figure 9 is a graph showing the rate of (a) OME 2 (b) OME 3 production from hydrogenation of CO 2 at temperatures (i) 100 °C (ii) 125 °C (iii) 150 °C (iv) 175 °C.
  • Figure 10 is a graph showing the rate of OMEi production from hydrogenation of CO and CO 2 at 150 °C.
  • the invention relates to converting CO and/or CO 2 into oxymethylene ethers in a single contacting step via the use of bifunctional nanomaterial catalyst or catalysts with an acidic support.
  • the OMEs include at least dimethoxymethane (OME or DME), as well as dimethoxymethane oligomers including OME 2 and OME3.
  • OME or DME dimethoxymethane
  • the formation of oligomers of dimethoxymethane, is advantageous as these can be more useful than dimethoxymethane as a diesel substitute.
  • the invention in another form, relates to converting either CO or CO 2 into dimethoxymethane (OME-i or DMM) in a single contacting step via the use of bifunctional nanomaterial catalyst or catalysts with an acidic support.
  • the invention uses a slurry phase reaction for hydrogenation of CO or CO2 for the production of OME1 with the aforementioned catalyst or catalysts. This process, which was carried out in a slurry reactor ( Figure 3), involves 2 reactions which take place in series ( Figure 1 ).
  • the catalyst or catalysts contain metallic sites (e.g. Ni, Ru, Pt, Cu, Pd, Rh or Re.
  • the Zeolite Beta 38, Beta 75 and Beta 150 supports are commercially available catalyst supports but others were made in lab via dealumination procedure to modify the acidity. To increase the Si/AI ratio dealumination was carried out by steam treating the as received zeolite beta followed by removal of dislodged aluminium.
  • Preferably at least 2 catalytic metals are used and the support is at least one of the group of zeolites, alumina, amorphous silica-alumina and silica.
  • the support material may comprise the above support material in conjunction with the ion exchange resin.
  • the metal/metals preferably are loaded onto the zeolite, alumina, amorphous silica-alumina or silica and the ion exchange resin is used to increase the acidity of the catalyst/catalyst support.
  • Described below is a procedure for the preparation of a Ni/Ru catalyst on an alumina substrate.
  • Nickel nitrate (Ni(NO 3 ) 2 .6H 2 O) (0 - 10.0 g), alumina (AI 2 O 3 ) (0 - 20.0 g) and chemicals such as RUCI3 (0 - 0.5 g) were used as the precursors for the catalyst synthesis.
  • the required amount of nickel nitrate was measured and dissolved in distilled water.
  • corresponding amount of alumina and metal promoter precursor were added into the solution.
  • the solution was heated up to 65 °C and maintained for 5hrs under constant stirring. The solutions were then dried overnight in a 100°C oven. Dry solid were recovered and calcined in a muffle furnace at 600 °C for 6 h under air atmosphere.
  • the catalyst loaded on the support is reduced by heating it to 400°C under H 2 /N 2 flow to reduce the metal oxide to pure metal state.
  • the person skilled in the art would be able to vary the precursor components and metal activation conditions to produce the required combination of catalytic metals loaded onto the support.
  • FIG. 1 is a graph showing the yield obtained from the hydrogenation of CO to dimethoxymethane with a single bifunctional catalyst Ru/Cu on zeolite support.
  • FIG. 4 is a graph showing the yield obtained from the hydrogenation of CO to dimethoxymethane with a single bifunctional catalyst Ru/Ni on a zeolite support.
  • dimethoxymethane can be produced by a single contacting step process by contact between synthesis gas containing CO and H 2 with a slurry of bifunctional catalyst and methanol.
  • Catalysts used in this work were synthesized using catalyst preparation method described above.
  • the catalytic activity of the resultant catalysts was evaluated using a slurry batch high pressure autoclave and the yield of OMEs were quantified using a Shimadzu 2014 GC equipped with ZB-1 capillary column.
  • catalysts were tested in this Example, these catalysts were: Ru-Ni/ ⁇ - Zeolite, Ru-Cu/ ⁇ -Zeolite, B-Ni/ ⁇ -Zeolite, Ru-Ni/y-alumina and monometallic Ru/ ⁇ - Zeolite.
  • Figure 7 illustrates the rate of OMEi production from hydrogenation of CO at temperatures of 50 °C, 80 °C, 100 °C, and 120 °C with (a) Ru-Ni/ ⁇ -zeolite, (b) Ru-Cu/ ⁇ - zeolite, (c) ⁇ - ⁇ / ⁇ -zeolite, and (d) Ru/ ⁇ -zeolite.
  • Figure 7 shows that OME can be produced with these catalysts in methanol as solvent and hydrogen, carbon oxides as reactants.
  • Figure 9 reports the rate of production of (a) OME 2 (b) OME 3 via hydrogenation of CO 2 at various temperatures.
  • Figure 10 shows the rate of production of OME from hydrogenation of CO x at 150 °C.
  • the results in Figure 10 indicate that the production rate of OME was at least one fold higher with CO 2 as reactant. This is thought to be as a result of the higher solubility of CO 2 gas in methanol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'éthers d'oxyméthylène comprenant les étapes de : a) mise en contact d'hydrogène gazeux et de CO et/ou CO2 avec un mélange de méthanol et d'un catalyseur dans des conditions de température et de pression permettant de supporter l'hydrogénation du gaz CO et/ou CO2 dans le gaz de synthèse en éthers d'oxyméthylène ; le catalyseur comprenant : i. un matériau catalytique qui est au moins un métal choisi dans le groupe constitué par Ni, Ru, Cu, Pt et Pd ; et ii. un support de catalyseur acide qui est au moins un support choisi dans le groupe des zéolites, de l'alumine, de la silice-alumine amorphe et de la silice ; et b) séparation des éthers d'oxyméthylène du catalyseur. L'invention concerne également un catalyseur pour la production de diméthoxyméthane à partir de gaz de synthèse dans une seule étape de mise en contact comprenant i. un matériau catalytique comprenant au moins un métal choisi dans le groupe constitué par Ni, Pt, Ru, Cu et Pd ; et ii. un support de catalyseur acide comprenant au moins un support choisi dans le groupe des zéolites, de l'alumine, de la silice-alumine amorphe et de la silice.
PCT/AU2018/050746 2017-07-17 2018-07-17 Production de diméthoxyméthane par hydrogénation directe Ceased WO2019014712A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2017902803 2017-07-17
AU2017902803A AU2017902803A0 (en) 2017-07-17 Dimethoxymethane production via direct hydrogenation

Publications (1)

Publication Number Publication Date
WO2019014712A1 true WO2019014712A1 (fr) 2019-01-24

Family

ID=65014814

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2018/050746 Ceased WO2019014712A1 (fr) 2017-07-17 2018-07-17 Production de diméthoxyméthane par hydrogénation directe

Country Status (1)

Country Link
WO (1) WO2019014712A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327444A (zh) * 2008-05-19 2008-12-24 中国科学院山西煤炭化学研究所 合成甲缩醛和甲酸甲酯的金属催化剂及其制法和应用
CN103570485A (zh) * 2012-07-20 2014-02-12 李坚 Co2或co的还原偶联反应制备丙烯、乙烯、乙醛酸、丙醇、乙醇、丙二醇、丙二酸酯等的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327444A (zh) * 2008-05-19 2008-12-24 中国科学院山西煤炭化学研究所 合成甲缩醛和甲酸甲酯的金属催化剂及其制法和应用
CN103570485A (zh) * 2012-07-20 2014-02-12 李坚 Co2或co的还原偶联反应制备丙烯、乙烯、乙醛酸、丙醇、乙醇、丙二醇、丙二酸酯等的方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BAHMANPOUR A. M. ET AL.: "Hydrogenation of Carbon Monoxide into Formaldehyde in Liquid Media", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 4, 2016, pages 3970 - 3977, XP055566383 *
BAHMANPOUR A.: "Single-step Conversion of Synthesis Gas into Formaldehyde", M. SC. THESIS, 2016, XP055567522 *
HEIM L. E. ET AL.: "Future perspectives for formaldehyde: pathways for reductive synthesis and energy storage", GREEN CHEMISTRY, vol. 19, 16 December 2016 (2016-12-16), pages 2347 - 2355, XP055567660 *
VLASENKO N. V. ET AL.: "Direct Single-Stage Conversion of Synthesis Gas to Dimethoxymethane: Influence of the Sequence of Metal Introduction into Cu, Pd- Zeolite Catalysts on the Degree of Cu and Pd Reduction and Catalyst Acidity", RUSSIAN JOURNAL OF APPLIED CHEMISTRY, vol. 76, 2013, pages 1615 - 1619, XP055566378 *

Similar Documents

Publication Publication Date Title
Guo et al. Recent advances in direct catalytic hydrogenation of carbon dioxide to valuable C 2+ hydrocarbons
US9656252B2 (en) Catalyst composition for producing hydrocarbons and method for producing hydrocarbons
US10960386B2 (en) Method and catalyst for producing methylbenzyl alcohol from ethanol by catalytic conversion
US10150718B2 (en) Hydrogen rejection in methanol to hydrocarbon process
EP2699346A1 (fr) Catalyseur utilisé pour produire des hydrocarbures
EP4399266A1 (fr) Production d'hydrocarbures de type gaz de pétrole liquéfié (gpl) à partir de charges contenant du dioxyde de carbone
JP3930879B2 (ja) 液化石油ガスの製造方法
KR20130074393A (ko) 효율적인 이산화탄소 전환 촉매 및 이의 제조 방법
Ahmad et al. Dimethoxymethane production via catalytic hydrogenation of carbon monoxide in methanol media
WO2006016444A1 (fr) Catalyseur de production de gaz de pétrole liquifié et procédé de production de gaz de pétrole liquifié en utilisant ce catalyseur
WO2014174107A1 (fr) Production d'hydrocarbures à partir d'un gaz de synthèse
JPS6123688A (ja) 合成ガスからの低級飽和脂肪族を主成分とする炭化水素の製造方法
KR20250027514A (ko) 수소 또는 수소 공급원과 결합되는 이산화탄소에서 액체 탄화수소의 생산
JP2010042344A (ja) 低級オレフィン製造用触媒、その製造方法及びこれを用いた低級オレフィンの製造方法
US20060242904A1 (en) Catalyst for producing liquefied petroleum gas, process for producing the same, and process for producing liquefied petroleum gas with the catalyst
WO2019014712A1 (fr) Production de diméthoxyméthane par hydrogénation directe
EP2699349A1 (fr) Catalyseur utilisé pour produire des hydrocarbures saturés à partir d'un gaz de synthèse
Bacariza et al. Sustainable Technologies in CO 2 Utilization: The Production of Synthetic Natural Gas
JP2007181755A (ja) 液化石油ガス製造用触媒、および、この触媒を用いた液化石油ガスの製造方法
Phongprueksathat et al. Enhancing Sustainability Through Heterogeneous Catalytic Conversions at High Pressure
WO2024129590A2 (fr) Conversion de gaz de synthèse de plateforme offshore
JPH0136811B2 (fr)
Zhang et al. Conversion of bio-syngas to liquid hydrocarbon over CuCoMn-Zeolite bifunctional catalysts
Inui et al. Selective gasoline synthesis from CO2 on a highly active methanol synthesis catalyst and an H-Fe-silicate of MFI structure
CN119016099A (zh) 一种双功能催化剂及其制备方法和应用

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: 18834781

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18834781

Country of ref document: EP

Kind code of ref document: A1