WO2018088736A1 - Catalyseur pour la préparation de méthoxyméthane à partir de gaz synthétique et son procédé de production - Google Patents

Catalyseur pour la préparation de méthoxyméthane à partir de gaz synthétique et son procédé de production Download PDF

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WO2018088736A1
WO2018088736A1 PCT/KR2017/011947 KR2017011947W WO2018088736A1 WO 2018088736 A1 WO2018088736 A1 WO 2018088736A1 KR 2017011947 W KR2017011947 W KR 2017011947W WO 2018088736 A1 WO2018088736 A1 WO 2018088736A1
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catalyst
precursor
zno
dimethyl ether
reaction
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Korean (ko)
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서영웅
정천우
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한양대학교 산학협력단
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    • 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
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers

Definitions

  • the present disclosure relates to a catalyst for producing dimethyl ether from synthesis gas and a process for producing the same. More specifically, the present disclosure relates to a catalyst capable of effectively converting synthesis gas produced by gasification of various raw materials into dimethyl ether, a method for preparing the same, and a method for preparing dimethyl ether using the catalyst.
  • Gasification process generally refers to a series of processes in which a carbonaceous raw material is reacted under the supply of a gasifying agent (e.g., oxygen, steam, carbon dioxide or a mixture thereof) to convert the main component into a synthesis gas consisting of hydrogen and carbon monoxide.
  • a gasifying agent e.g., oxygen, steam, carbon dioxide or a mixture thereof
  • carbonaceous raw material broadly includes solid, liquid, and gaseous carbonaceous materials that can be used to generate synthesis gas.
  • Such carbonaceous materials are not necessarily limited to a specific kind, but biomass (botanical and animal materials such as herbaceous and woody materials), coal (anthracite, bituminous coal (reverse coal, lignite, peat, etc.), lower activated carbon, etc.) , Organic waste, sail oil, coke, tar and the like can be exemplified.
  • Coal a representative raw material for the gasification process, is distributed in large quantities in a wide range of regions around the world, and is re-emerged as a fuel source to replace petroleum depletion that is widely used to date.
  • biomass which has recently been in the spotlight, can also provide basic oils of various fuels and platform compounds through various treatment processes, and this technology is also known to be applied as a raw material for gasification reaction.
  • the gasification process technology is not only a technology for producing raw materials and fuels of various compounds, but also its application range is extended to areas such as power generation.
  • it can be applied to hydrogen power generation, ammonia production, refinery process using hydrogen in synthesis gas, which is the main product of gasification process, and diesel using synthesis gas as raw material of Fischer-Tropsch reaction.
  • Oil, jet oil, lube base oil, naphtha, etc. can be manufactured.
  • dimethyl ether (CH 3 OCH 3 ) is not only similar to propane and butane, which are main components of LPG, in physical and chemical properties, but also excellent in many respects.
  • it can be used as an aerosol propellant, a substitute for diesel fuel, an intermediate of chemical reactions, and the like, and is an oxygen-containing compound that has recently attracted attention.
  • it is of great utility as a clean fuel that is easy to transport and store.
  • the synthesis gas is converted into methanol through a hydrogenation reaction as shown in Scheme 4 below (methanol synthesis reaction), and the methanol synthesized as in Scheme 5 is converted into dimethyl ether through a dehydration reaction. It involves a reaction to convert (methanol dehydration).
  • methanol is produced from the synthesis gas in the presence of a typical methanol synthesis catalyst such as a Cu / ZnO / Al 2 O 3 catalyst.
  • a typical methanol synthesis catalyst such as a Cu / ZnO / Al 2 O 3 catalyst.
  • the alumina (Al 2 O 3 ) component is contained in a small amount as a promoter.
  • the hydrophilic solid acid catalyst eg, zeolite (J. Am. Chem. Soc., 132 (2010) 8129-8136)
  • gamma-alumina eg, US patent
  • silica-alumina eg, US Pat. No. 4,885,405
  • a plurality of reactions ie methanol synthesis, water gas shift and dehydration
  • the ingredients such as zeolite, ⁇ - alumina after the pre-prepared Cu 2 +, Zn 2 +, Al 3 + is a method of synthesizing by injecting the co-precipitation of the metal precursor, such as is also known (Fuel Proc. Tech., 121 (2014) 38-46).
  • the sol in order to introduce an acid function-gel method (.. Catal Commun, 8 ( 2007) 598-606) to that used in a technique for introducing the Al 3 +, using a precipitating agent known to NaAlO 2 bar, wherein the oxalic acid ( oxalate acid) and ethanol need to be used additionally.
  • the dehydration catalyst in which the acid function is introduced needs to be introduced through zeolite or gamma-alumina as a seed, or may be purchased from another manufacturer.
  • the acid functions without using a seed material injected into the Al 3 + has lead to the complexity of the process, and has a problem in that the catalyst efficiency goes down.
  • a process of preparing dimethyl ether from a synthesis gas is generally performed in a multistage process of a hydrogenation reaction-dehydration reaction.
  • An object of the present invention is to provide a Cu / ZnO / Al 2 O 3 based catalyst having excellent methanol conversion of syngas through hydrogenation and dimethyl ether conversion of methanol by dehydration.
  • another embodiment of the present disclosure is to provide a process for producing dimethyl ether with high yield and high selectivity from synthesis gas in the presence of the catalyst described above.
  • a method for preparing a Cu / ZnO / Al 2 O 3 based catalyst comprising a.
  • the second catalyst precursor is substantially free of hydrotalcite crystal structure.
  • the first catalyst precursor may exhibit an XRD pattern that does not contain peaks with 2 ⁇ ranging from 10 to 14 °.
  • the second catalyst precursor does not release CO 2 upon pyrolysis treatment at a temperature of at least 500 ° C.
  • step b) is
  • b2) may first comprise aging the precipitate produced in step b1) to form a first catalyst precursor.
  • said step c) may be carried out after the pH decrease takes place in step b2).
  • the step c) is
  • step c2) secondary aging of the precipitate produced in step c1) to form a second catalyst precursor comprising Cu x Zn 1 - x (OH) 2 CO 3 and Al (OH) 3 ;
  • Cu / ZnO / Al 2 O 3 based catalyst comprising crystalline Cu / ZnO and amorphous Al 2 O 3 as active ingredients
  • the catalyst comprises 30 to 60% Cu, 10 to 30% Zn and 13 to 40% Al on an atomic basis,
  • Amorphous Al 2 O 3 is dispersed in the surface of crystalline Cu / ZnO and / or is present in a form that at least partially covers, and
  • a catalyst is provided having a specific surface area of Cu in the range of 10 to 35 m 2 / g.
  • the atomic ratio of Cu / Zn in the catalyst may range from 50/50 to 80/20.
  • the Cu / ZnO / Al 2 O 3 based catalyst may be present in the form of an amorphous Al 2 O 3 shell on the crystalline Cu / ZnO core.
  • the product contains methanol and dimethyl ether, wherein the molar ratio of dimethyl ether to methanol may range from 0.05 to 4.
  • the step of separating dimethyl ether from the product may be carried out by liquefaction or distillation.
  • the method may further include combining the reactant with components other than the separated dimethyl ether in the product.
  • the single reactor is a continuous reactor and the reaction of the synthesis gas may be carried out under a space velocity (GHSV) condition of 1,000 to 100,000 cm 3 g cat ⁇ h ⁇ 1 .
  • GHSV space velocity
  • FIG. 1 is a diagram conceptually showing the morphological characteristics of a Cu / ZnO / Al 2 O 3 based catalyst according to one embodiment of the present disclosure
  • FIG. 2 is a diagram illustrating composition and morphological changes when treating a second catalyst precursor containing Cu, Zn and Al in the order of a calcination step and a reduction step, according to one embodiment of the disclosure;
  • FIG. 3 is a schematic illustration of an example of a process for preparing dimethyl ether from synthesis gas in a single reaction mode using a catalyst according to one embodiment of the present disclosure
  • Example 5 is a graph showing a change in pH over time during the preparation of a catalyst according to Example SP and a catalyst according to Comparative Examples CZ and CP, respectively;
  • Example 6 is a graph showing the results of XRD analysis on the catalyst precursor formed during the preparation of the catalyst according to Example (SP) and the catalyst according to Comparative Examples (CZ and CP), respectively;
  • Example 7 is a graph showing the results of TGA analysis for the thermal stability evaluation of the catalyst precursor formed during the preparation of the catalyst according to Example (SP) and the catalyst according to Comparative Examples (CZ and CP), respectively;
  • Example 8 is a graph showing the results of XRD analysis for the catalyst in the form of oxide according to the catalyst according to Example (SP) and Comparative Examples (CZ and CP) respectively;
  • FIG. 9 is a graph showing the results of performing IPA-TPSR analysis while varying the Al content to evaluate the amount of acid point in the catalyst in the oxide form according to the catalyst according to Example (SP) and Comparative Example (CP), respectively. ;
  • FIG 10 is a graph showing methanol yield in the reaction for converting synthesis gas to methanol in the presence of a catalyst according to each of Examples (SP) and Comparative Examples (CZ and CP);
  • synthetic gas means a mixed gas that is typically produced by a gasification reaction and contains CO and H 2 principal components, and may further include CH 4 and / or CO 2 .
  • crystalline or “crystalline” can mean any solid material typically arranged to have a valence lattice structure (eg, three-dimensional order), generally X It can be specified by -ray diffraction analysis (XRD), nuclear magnetic resonance analysis (NMR), differential scanning calorimetry (DSC) or a combination thereof.
  • XRD -ray diffraction analysis
  • NMR nuclear magnetic resonance analysis
  • DSC differential scanning calorimetry
  • amorphous or “amorphous” can mean any solid material that lacks a lattice structure (eg, three-dimensional regularity), as opposed to "crystalline” or “crystalline”. to be.
  • FIG. 1 conceptually illustrates the morphological characteristics of a Cu / ZnO / Al 2 O 3 based catalyst according to one embodiment of the disclosure.
  • the catalyst is typically a three component catalyst containing three metal components as the active component.
  • the composition may further include other components (eg, binder or matrix components) that do not substantially affect the basic catalytic activity.
  • Cu and ZnO are evenly distributed while intimately contacting each other at the core portion of the catalyst in a state of showing crystallinity.
  • Cu is present in a reduced form as a whole by a reduction treatment after oxidation, while Zn is present in an oxide form, and thus Cu may be expressed as Cu / ZnO.
  • alumina Al 2 O 3
  • alumina has an amorphous property and is dispersed in the surface of crystalline Cu / ZnO and / or exists in the form of at least partially covering.
  • the term "dispersed on the surface” is to be understood in a comprehensive sense, and in some cases may include a depth from the surface, for example up to about 75 nm (specifically up to about 50 nm). (E.g., when Al is present in a rich state from the Cu / ZnO surface to a certain depth).
  • the thickness of the coating layer (or shell) is, for example, about 25 to 100 nm, specifically about 27 to 75 nm. And more specifically in the range of about 30-50 nm.
  • the particle size of the Cu crystal in the catalyst may range from, for example, about 4 to 8 nm, specifically about 4.5 to 7 nm, more specifically about 4.8 to 6.5 nm.
  • the Cu / ZnO / Al 2 O 3 based catalyst when the alumina (Al 2 O 3 ) is partially coated on the Cu / ZnO core, the alumina (Al 2 O 3 ) is aggregated into a band (or band) form or small in size. It can exist as is.
  • the Cu / ZnO / Al 2 O 3 based catalyst may be present in the form of an amorphous Al 2 O 3 shell formed on the crystalline Cu / ZnO core.
  • the Cu / ZnO / Al 2 O 3 based catalyst contains about 30 to 60%, specifically about 35 to 55%, more specifically about 40 to 50% Cu on an atomic basis.
  • Zn is contained in about 10 to 30%, specifically about 13 to 28%, more specifically about 15 to 25%.
  • the ratio of Cu / Zn (atomic basis) is for example in the range of about 50/50 to 80/20, specifically about 60/40 to 75/25 and more specifically about 65/35 to 70/30. This is because it is suitable for forming Cu x Zn 1-x (OH) 2 CO 3 as a catalyst precursor as described below in the ratio range of Cu / Zn.
  • the content of Al in the catalyst may be in the range of about 13 to 40%, specifically about 15 to 35%, more specifically about 20 to 30% on an atomic basis, so that the dehydration reaction of methanol should be at an appropriate level.
  • the acid point required for the synthesis of dimethyl ether can be ensured.
  • the Cu / ZnO: Al catalyst for conventional methanol synthesis contains only a small amount of Al (for example, about 3%) to act as a promoter, but significantly in this embodiment. Contains high levels.
  • the Cu / ZnO / Al 2 O 3 based catalyst according to this embodiment has a morphological characteristic in which amorphous Al 2 O 3 surrounds the surface (or surroundings) of crystalline Cu / ZnO as described above.
  • Cu specific surface area which is an indicator of hydrogenation activity, is not significantly affected. Therefore, the synthesis gas undergoes a cascade or tandem transformation process (hydrogenation-dehydration reaction). Can be easily converted to dimethyl ether.
  • the specific surface area of Cu in the catalyst may range from about 10 to 35 m 2 / g, specifically about 15 to 32 m 2 / g, more specifically about 20 to 30 m 2 / g, as described above.
  • the synthesis gas as a feedstock can easily access a catalytic site having a hydrogenation function.
  • the specific surface area of the catalyst (or precursor catalyst) can be measured by N 2 O-RFC (reactive frontal chromatography). Such specific surface area measurement techniques are described in detail in Angew. Chem. Int. Ed., 53 (2014) 7043-7047, which is incorporated herein by reference.
  • a method for preparing a Cu / ZnO / Al 2 O 3 based catalyst for converting synthesis gas into dimethyl ether is provided, which will be described in more detail below.
  • the use of available Cu 2 + precursor may include a water-soluble copper salt such as copper nitrate, copper sulfate, copper acetate, formate, copper chloride (II), copper, copper iodide, used alone, or two It can use combining a species or more.
  • the as Zn 2 + precursor for example, zinc nitrate, zinc sulfate, zinc acetate, formate, zinc chloride (II), zinc may be used a water-soluble zinc salt such as zinc iodide, alone or in combination of two or more It can be used in combination.
  • the input amount between the Cu 2 + precursor and the Zn 2 + precursor may be adjusted to meet the content range of Cu and Zn in the final catalyst (element-based), and further, in the ratio range of Cu / Zn as described above.
  • the concentration of the total metal precursors (Cu precursor and Zn precursor) in the solution is, for example, adjustable in the range of about 0.1 to 1.5 M, specifically about 0.5 to 1.4 M, more specifically about 1 to 1.2 M.
  • a precipitant in particular a basic precursor, may be used to form the solid Cu / Zn precursor.
  • the precipitant which may be used may include carbonates or bicarbonates of alkali metals (lithium, sodium, potassium, etc.) or ammonium, and these may be used alone or in combination.
  • a precipitant solution specifically an aqueous precipitant solution, is prepared separately from the preparation of the metal (Cu and Zn) precursor solutions described above.
  • the concentration of precipitant in the precipitant solution may be, for example, in the range of about 0.01 to 1.2 M, specifically about 0.05 to 1 M, more specifically about 0.1 to 0.5 M.
  • a process of inducing precipitation of Cu and Zn is performed by combining (adding) the metal precursor solution to the precipitant solution.
  • This precipitation process involves heating the precipitant solution, for example, to a temperature range of about 20 to 90 ° C., specifically about 50 to 80 ° C., more specifically about 60 to 70 ° C., followed by addition of the metal precursor solution (specifically, It can be done in such a way).
  • the amount (based on weight) of the metal (Cu and Zn) precursor / precipitant may be adjusted within a range of, for example, about 0.5 to 2, specifically about 1 to 1.8, and more specifically about 1.1 to 1.5.
  • amorphous initial particles are formed by adding the metal precursor (or metal precursor solution) to the precipitant solution.
  • a first aging step of the precipitate in the solution (combination solution) in which the metal precursor solution and the precipitant solution are combined is performed.
  • amorphous initial particles are converted into a crystalline form, and the process is performed.
  • the pH of the combined solution (or Cu and Zn-containing precipitates) is reduced.
  • it refers to a crystallization product of Cu + 2 and Zn 2 + precursor precursor as "first catalyst precursor.”
  • a decrease in pH in the combined solution or precipitate indicates that the initial particles consisting of the Cu precursor and the Zn precursor were converted from amorphous to crystalline.
  • the catalyst precursor (the first catalyst precursor) having a desired crystal properties by the addition of Al 3 + precursor after the point at which the pH is reduced in the aging process.
  • the pH can be added to the Al 3 + precursor after, for example, down to the extent of at least about 0.1, at least about 0.07, more specifically at least about 0.05, specifically.
  • the aging step (primary aging step) can be performed, for example for at least about 15 minutes, specifically about 20 to 180 minutes, more specifically about 30 to 90 minutes.
  • the aging temperature can be adjusted, for example, in the range of about 20 to 90 ° C, specifically about 40 to 80 ° C, more specifically about 60 to 70 ° C.
  • the first catalyst precursor has a crystalline structure represented by Cu x Zn 1 - x (OH) 2 CO 3.
  • 2 ⁇ is about 10 to 14 °, Specifically, it is preferable not to contain a peak having 2 ⁇ of about 11 to 13 °, more specifically 2 ⁇ of 11.5 to 12 °.
  • Al 3 + precursor can be mentioned aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum iodide such as, can be used alone or in combination.
  • Al 3 + precursor solution (specifically, an aqueous solution) bars which can be added in the form, its concentration is, for example, about 0.1 to 1.5 M, particularly about 0.5 to 1.2 M, more specifically about 0.8 to 1 M Adjustable within the range.
  • the addition of Al 3 + precursor to form a precipitate, and further performing a secondary aging step to form a second catalyst precursor may be selected in consideration of the Al content range in the final catalyst as described above.
  • the temperature conditions of the precipitation and the secondary aging step according to the addition of Al 3 + precursor may be set the same or similar to the first catalyst precursor forming step.
  • the further aging step (secondary aging step) can be carried out, for example, for at least about 15 minutes, specifically about 20 to 180 minutes, more specifically about 30 to 90 minutes.
  • a second catalyst precursor precursor Cu 2 +, Zn 2 + and Al precursors in the 3+ precursor catalyst precursor is typically formed by precipitation with (Cu, Zn, Al) hydrotalcite crystal structure, that is, Cu 3 Zn 3 Al 2 (OH) 16 CO 3 OH H 2 O and has a different characteristic from that shown.
  • the second catalyst precursor is present in a mixture of crystalline form (Cu x Zn 1- x ) (OH) 2 (CO 3 ) and amorphous Al (OH) 3. It seems to be.
  • the second catalyst precursor is distinguished from a precursor having a hydrotalcite structure in terms of thermal stability, for example, when pyrolyzed at a temperature of at least about 500 ° C., specifically at least about 550 ° C., more specifically at least about 570 ° C. It does not emit CO 2 .
  • a thermal decomposition temperature typically about 600 to 700 ° C.
  • the second catalyst precursor prepared as described above optionally undergoes a drying step, with typical drying temperatures ranging from about 80 to 120 ° C. (specifically about 95 to 110 ° C., more specifically about 100 to 105 ° C.). Can be. Thereafter, the dried second catalyst precursor (containing Cu, Zn and Al) is treated in the order of the calcination step and the reduction (activation) step as shown in FIG. 2 to change the composition and morphological characteristics, thereby changing Cu / ZnO / Al 2 O 3 -based catalyst will be formed.
  • the calcination step is carried out under the conditions of an oxygen-containing atmosphere (eg air) to convert the metal components contained in the second catalyst precursor into the oxide form (ie CuO / ZnO / Al 2). Mixed oxides of O 3 ).
  • an oxygen-containing atmosphere eg air
  • the calcination temperature can be adjusted, for example, in the range of about 300 to 700 ° C. (specifically about 350 to 500 ° C., more specifically about 400 to 450 ° C.) under the supply of oxygen (air).
  • exemplary calcination times may range from, for example, about 2 to 7 hours, specifically about 3 to 6 hours.
  • the heating rate during the calcination process may be, for example, about 0.1 to 20 °C / min, specifically about 2 to 10 °C / min range.
  • the catalyst converted to the oxide by the calcination step forms a Cu / ZnO / Al 2 O 3 -based catalyst by a reduction (activation) treatment, wherein the reduction treatment converts the oxide catalyst to a reducing gas (eg hydrogen and / or carbon monoxide).
  • a reducing gas eg hydrogen and / or carbon monoxide
  • the reducing gas may be introduced and treated in the form of a mixed gas combined with an inert gas (nitrogen, argon, etc.).
  • the reduction treatment may be performed for about 1 to 24 hours under a temperature of about 250 to 350 ° C. (specifically about 270 to 320 ° C.) and a pressure of about 1 to 200 atmospheres (specifically about 10 to 100 atmospheres). Can be.
  • the Cu / ZnO / Al 2 O 3 -based catalyst can be effectively applied to a process using a single reactor because of the high activity of converting the synthesis gas into dimethyl ether.
  • the reaction conditions may be determined in consideration of the conversion of methanol in the reactor (specifically, a single reactor) and the conversion into dimethyl ether from a thermodynamic point of view, and typically, about 200 to 400 ° C., more typically about It may range from 230 to 350 ° C.
  • the reaction pressure it can be appropriately adjusted in consideration of reaction operability, for example, may be about 1 to 100 atm, specifically about 5 to 50 atm.
  • FIG. 3 shows a process for preparing dimethyl ether from synthesis gas in a single reaction mode using a catalyst according to one embodiment of the present disclosure.
  • the feedstock synthesis gas mainly contains hydrogen and carbon monoxide and may further comprise CH 4 and / or CO 2 .
  • the molar ratio of H 2 / CO in the synthesis gas may, for example, range from about 1 to 10, specifically about 1.5 to 5, more specifically about 1.8 to 3. If the amount of hydrogen does not reach the desired level, it is possible to increase the proportion of hydrogen in the feedstock by adding a water gas shift reaction (WGS) step in front of the reactor.
  • WGS water gas shift reaction
  • dimethyl ether may be prepared by batch and continuous modes, but in consideration of economical efficiency, such as continuous mode is preferred.
  • the reactor is not particularly limited, but, for example, a gaseous fixed bed reactor, a fluidized bed reactor, or the like may be used, and a fixed bed reactor may be advantageous.
  • the gas hourly space velocity (GHSV) is determined by comprehensively considering the productivity and the conversion rate through catalytic contact. If too low, the productivity will be decreased, whereas if too high, the contact of the catalyst will be insufficient. will be.
  • the space velocity is, for example, about 1,000 to 100,000 cm 3 g cat ⁇ h ⁇ 1 , specifically about 1,500 to 20,000 cm 3 g cat ⁇ h ⁇ 1 , more specifically 2,000 to 10,000 cm 3 g cat ⁇ h May range from -1 .
  • the unreacted feedstock may be introduced into the reactor in combination with the new feedstock by separating and recycling the dimethyl ether conversion process.
  • it may be advantageous to recycle after separating and removing the water generated by the dehydration reaction.
  • the product may also contain methanol which is not converted to dimethylether during the reaction.
  • the CO conversion can be, for example, in the range of about 10 to 80%, specifically about 20 to 70%, more specifically about 40 to 65%, and the selectivity of dimethyl ether is about 5 to 85%, Specifically about 20 to 80%, more specifically about 40 to 70%.
  • the molar ratio of dimethylether / methanol in the reaction product may, for example, range from about 0.05 to 4, specifically from about 0.25 to 3, more specifically from about 0.25 to 2.5.
  • distillation for example, distillation using a separation-wall column
  • gas-liquid separation dimethyl ether separation through methanol liquefaction
  • dimethyl ether can be separated off and recovered and the remaining product can be recycled and introduced into the reactor with the fresh feedstock.
  • At least two reactors are used because they mainly show a conversion activity to methanol.
  • the synthesis gas is converted into methanol, while in the first reactor,
  • acid catalysts such as a zeolite
  • a conventional catalyst preparation method co-precipitation, CP.
  • Cu 2 + precursor in accordance with each of the Al content of Cu (NO 3) 2 ⁇ 3H 2 O, Zn 2 + as a precursor Zn (NO 3) 2 ⁇ 6H 2 O, and Al 3 + as Al (NO 3) precursor 3 9H 2 O was separately prepared, then dissolved in 175.0 mL H 2 O and injected at once. 4,200 mL H 2 O was prepared in a 5 L glass vessel, 42.77 g of NaHCO 3 was dissolved as precipitant and the temperature was set to 70 ° C. When reaching the set temperature, the Cu + 2 and Zn 2 + precursor the precursor is a metal-containing precursor solution was injected into 14 mL / min using a master flex (masterflex).
  • the metal precursor solution was aged for 90 minutes, after which the precipitated material was recovered. In order to remove Na + and NO 3 ⁇ in the precipitate, a total of four washing and filtering processes were repeated and dried in an oven set at 105 ° C. for 12 hours.
  • the space velocity (GHSV) is 2,000 cm3 kg cat -1 h - said been 1
  • the product was analyzed by FID (flame ionized detector) of the on-line GC (gas chromatography) .
  • FID flame ionized detector
  • SP-13 with an Al content of 13% was prepared using sequential precipitation (SP) as follows:
  • a catalyst was prepared by preparing a metal precursor solution in accordance with the molar ratio of the metal.
  • a reaction was performed in which dimethyl ether was converted from the synthesis gas under the same reaction conditions except that the Cu / ZnO / Al 2 O 3 based catalyst prepared in Example 1 was used as the catalyst.
  • the results are shown in Table 1 and FIG. 4 (CO conversion: green bar, DME selectivity (red bar), DME yield of SP catalyst: blue filled circle, and CP catalyst).
  • DME yield shown in blue blank circle.
  • the contents of Cu, Zn and Al were analyzed using ICP-AES, wherein the Cu / Zn ratio was fixed at about 70:30.
  • the Al content ratio was up to about 5.6% from 13%, 30% and 40% of the set content, but was prepared to approximate the set content as a whole.
  • dimethyl ether compared to the catalysts according to Comparative Example 1 of the same composition (CP-13, CP-30 and CP-40) It was confirmed that the production rate of was increased by about 2 to 3 times. Specifically, when using the catalyst of Example 1 (SP-13) having an Al content of 13% dimethyl ether production rate is 115.4 g kg cat -1 h -1 when using the catalyst of Comparative Example 1 (CP-13) The production rate of dimethyl ether increased more than three times compared to 31.8 g kg cat -1 h -1 .
  • the production rate of dimethyl ether was 433.0 g kg cat -1 h -1 and 389.8, respectively. g kg cat -1 h - 1 .
  • the hydrogenation reaction which is the first reaction in the multistage reaction, exhibits different activities depending on the crystal structure of the catalyst precursor. That is, in the catalyst preparation method according to Example 1, the catalyst precursor does not form a (Cu, Zn, Al) hydrotalcite structure ((Cu 3 Zn 3 Al 2 (OH) 16 CO 3 )), so as to favor the activity As a result of the presence of the crystalline form (Cu x Zn 1- x ) (OH) 2 (CO 3 ) and amorphous Al (OH) 3 in a mixed form, it is determined that the CO conversion is increased.
  • Example 1 in a more improved acid function by adding a metal precursor 3 + Al after formation of the crystalline form (Cu x Zn 1 -x) ( OH) 2 (CO 3) , and thus there is a precipitate containing additionally Al- It can be seen to increase the selectivity of dimethyl ether because it can be expressed.
  • Example 1 in which the Al precursor is simultaneously added with the Cu precursor and the Zn precursor, the above-described form was not observed.
  • Example 1 since the initial particles composed of Cu and Zn are converted to a crystalline form, the Al precursor solution is added to prepare a catalyst, and thus a phenomenon of decreasing pH can be observed.
  • Example 1 the reflection of the catalyst precursor at 14.66 °, 17.49 °, 24.11 ° and 32.32 ° was similar to that of the precursor (combination catalyst precursor) in Comparative Example 3 (CZ).
  • (20-1) -d-spacing (2.768 kPa) at 32.32 ° for Comparative Example 3 (CZ) precursor was in the range of 32.06 to 32.31 ° despite the addition of significant amounts of Al.
  • the corresponding d (20-1) value of 2.768-2.808 kV means that the precursor of the SP catalyst consists of a Cu / Zn atomic ratio of 70/30 to 80/20. Therefore, the addition of the Al precursor has little effect on the crystalline structure, which can be seen as the particles grew considerably during the aging process.
  • HT-CO 3 high-temperature carbonate
  • the catalyst precursor SP according to Example 1 is substantially free of CO 2 , especially in the thermal decomposition temperature zone of at least 500 ° C. Specifically, the thermal decomposition at 200 to 250 ° C. for the precursor of the catalyst (SP-40) of Example 1 releases H 2 O from Al (OH) 3 as supported by the thermal decomposition of pure Al precipitates. Corresponds to However, in the case of the SP-13 catalyst, since the hydrotalcite crystal was partially contained, a small amount of CO 2 was released even in the pyrolysis temperature range exceeding 500 ° C.
  • the catalyst precursor When the catalyst precursor is subjected to a heat treatment (firing) step, it is converted into a metal oxide form.
  • the XRD analysis is performed while changing the Al content of the catalyst (SP) of Example 1 and the catalysts (CZ and CP) of Comparative Examples 1 and 3. Was performed. The results are shown in FIG.
  • the width of the peak decrease was significantly increased, which is high thermal of the (Cu, Zn, Al) hydrotalcite crystal structure. It may be due to the stability.
  • a metal oxide catalyst having sufficient crystallinity in the form of CuO could be prepared. That is, the oxide catalyst prepared according to Example 1 has higher crystallinity than the catalyst according to the conventional production method (Comparative Example 1).
  • the acid point of the catalyst (SP) of Example 1 and the catalyst (CP) of Comparative Example 1 was evaluated.
  • the acid point of the catalyst can be evaluated relatively by the temperature-programmed surface reaction of isopropanol, ie iso-propanaol temperature-programmed surface reaction (IPA-TPSR).
  • IPA-TPSR is a technique for analyzing acid sites by identifying propylene fragments that are desorbed at elevated temperatures after adsorption of iso-propanol. 121-137), which is incorporated herein by reference.
  • the relative amount of acid point is the ratio of the acid point (A SP ) of the catalyst of Example 1 to the acid point (A CP ) of the catalyst of Comparative Example 1, and the total acid point, strong acid point and weak acid point (Ra T , Ra S and Ra W). ) was evaluated. The results are shown in Table 2 and FIG.
  • the ratio of the strong acid point Ra S at low temperature increased by approximately 3 times as the Al content increased.
  • the weak acid point ratio (Ra W ) the Al content showed a tendency to increase slightly.
  • the acid point of the catalyst (SP) prepared according to Example 1 was more than two times higher than that of the catalyst (CP) prepared according to Comparative Example 1, thereby increasing the production rate of dimethyl ether by methanol dehydration reaction. It can be expected to be done.
  • Example 1 Comparative Example 1 CZ 27.9 ⁇ 2.3 13% Al 28.5 ⁇ 2.0 32.2 ⁇ 3.2 30% Al 28.8 ⁇ 2.3 14.8 ⁇ 2.2 40% Al 24.4 ⁇ 2.0 14.5 ⁇ 2.7
  • the specific surface area of copper was 32.2 m 2 with increasing Al content. g -1 to 14.5 m 2 significantly reduced to g ⁇ 1 .
  • the copper specific surface area of the catalyst of Example 1 is 28.5 m 2 g -1 , 28.8 m 2 g -1 , and 24.4 m 2 There was no significant decrease as g ⁇ 1 .
  • the catalyst prepared according to Example 1 was able to maintain a high copper specific surface area in spite of an increase in Al content, and thus exhibited a copper specific surface area more than two times higher than that of the catalyst prepared according to Comparative Example 1.
  • GHSV space velocity
  • the catalyst (SP) of Example 1 showed a significantly higher methanol yield, especially at Al 30% and Al 40%, compared to the catalyst (CP) of Comparative Example 1.
  • the catalyst (SP) of Example 1 was prepared in Comparative Example 1 in both methanol synthesis and dehydration reaction. It can be seen that it has higher activity than the catalyst (CP). That is, the catalyst of Example 1 can exhibit more improved STD conversion activity because it contains higher copper specific surface area and more acid point.
  • the catalyst (CP-30) of Comparative Example 1 is in a form in which Cu, Zn, and Al are evenly dispersed.
  • the catalyst (CP-30) of Comparative Example 1 is in a form in which Cu, Zn, and Al are evenly dispersed.
  • the catalyst (CP-30) of Comparative Example 1 is in a form in which Cu, Zn, and Al are evenly dispersed.
  • the catalyst (CP-30) of Comparative Example 1 is in a form in which Cu, Zn, and Al are evenly dispersed.
  • Cu and Zn are evenly dispersed in the particles
  • Al is agglomerated in a band form or a small size in the outer portion of the particles (arrows s and a are respectively of the amorphous alumina) Shell and small aggregates).
  • the catalyst prepared according to Example 1 is present in a form in which Al is dispersed in the periphery of Cu / Zn particles or aggregated into small particles, rather than a form in which Cu, Zn and Al are evenly dispersed.

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  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

La présente invention concerne : un catalyseur à base de Cu/ZnO/Al2O 3, qui est produit sans effectuer un changement important dans un procédé de production de catalyseur classique alors qu'un matériau d'amorce, tel qu'une zéolite ou une gamma-alumine, et/ou d'autres matériaux ne sont pas ajoutés; un procédé de production de celui-ci; et un procédé de préparation efficace de méthoxyméthane à partir de gaz synthétique en présence du catalyseur.
PCT/KR2017/011947 2016-11-09 2017-10-27 Catalyseur pour la préparation de méthoxyméthane à partir de gaz synthétique et son procédé de production WO2018088736A1 (fr)

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KR102296609B1 (ko) * 2019-12-19 2021-09-02 재단법인 포항산업과학연구원 탄화수소 제조용 촉매 및 이의 제조 방법

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