WO2013072197A1 - Methanol synthesis catalyst on the basis of copper, zinc and aluminum - Google Patents

Methanol synthesis catalyst on the basis of copper, zinc and aluminum Download PDF

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Publication number
WO2013072197A1
WO2013072197A1 PCT/EP2012/071581 EP2012071581W WO2013072197A1 WO 2013072197 A1 WO2013072197 A1 WO 2013072197A1 EP 2012071581 W EP2012071581 W EP 2012071581W WO 2013072197 A1 WO2013072197 A1 WO 2013072197A1
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Prior art keywords
catalyst
catalyst precursor
precursor material
copper
content
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PCT/EP2012/071581
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English (en)
French (fr)
Inventor
Malte Behrens
Benjamin KNIEP
Patrick KURR
Robert SCHLÖGL
Martin Hieke
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Süd-Chemie Ip Gmbh & Co. Kg
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Priority to CN201280064200.2A priority Critical patent/CN104039444A/zh
Priority to EP12783572.6A priority patent/EP2780110A1/en
Priority to JP2014541598A priority patent/JP2015502248A/ja
Priority to IN985KON2014 priority patent/IN2014KN00985A/en
Priority to RU2014123678/04A priority patent/RU2014123678A/ru
Publication of WO2013072197A1 publication Critical patent/WO2013072197A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts 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
    • B01J23/80Catalysts 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391Physical properties of the active metal ingredient
    • B01J35/392Metal surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391Physical properties of the active metal ingredient
    • B01J35/393Metal or metal oxide crystallite size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/61310-100 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66Pore distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16Reducing
    • B01J37/18Reducing with gases containing free hydrogen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15Preparation 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
    • C07C29/151Preparation 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
    • C07C29/153Preparation 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 characterised by the catalyst used
    • C07C29/154Preparation 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 characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst containing
  • Cu/Zn molar ratios of less than 2.8 are essential in achieving relatively small and catalytically particularly active copper crystallite sizes.
  • This document also teaches that the aluminum oxide component is obtained at least in part from an aluminum hydroxide sol .
  • US 4,279,781 discloses a low temperature methanol synthesis catalyst comprising copper and zinc oxide in a ratio
  • the catalyst includes, preferably, a thermal stabilizing metal oxide such as aluminum oxide in minor proportions and is prepared by co- precipi ation of all three constituents from a single
  • composition of the ZnO/Al2C>3 phase surrounding the particles .
  • the catalyst of US 3,923,694 seems to be free of carbonate as its precursor characterized as comprising 10 to 80% copper with the balance essentially being the crystalline spinel structure.
  • the catalyst of US 3,850,850 seems to have an inhomogeneous structure as it is taught in the two examples that only 67% and 75.3%,
  • the hydrogenation catalyst of EP 0 522 66.9 A2 is prepared in a process comprising the steps of a ⁇ preparing a first aqueous solution containing at least one water-soluble copper salt and at least one water- soluble zinc salt, b) preparing a second solution containing at least one
  • water-soluble basic aluminum salt such as sodium
  • insoluble solid is formed, d) recovering the insoluble solid, and e) calcining the recovered solid.
  • the recovered precipitate is calcined at a temperature in the range of from about 475 ° C to about 700 ° C for periods of about 30 to about 120 minutes. Under these conditions, metal carbonate still existing in the insoluble solid recovered in step d) is converted to oxide under release of carbon
  • One further object of the present invention is to provide a new methanol synthesis catalyst (material) showing an excellent catalytic activity and stability.
  • One further object of the present invention resides in providing a preparation method for the catalyst precursor material, the catalyst material and the corresponding catalys .
  • a Cu/Zn/Al catalyst precursor material comprising oxides and carbonates of copper, zinc and aluminum wherein copper and zinc are present together in a greater molar amount than aluminum, and
  • the standard deviation of the local molar Al content, as measured by EDX, is not more than 50% .
  • a Cu/Zn/Al catalyst precursor material comprising oxides and carbonates of copper, zinc and aluminum wherein copper and zinc are present together in a greater molar amount than aluminum, and wherein the reduction of this precursor material in the presence of hydrogen leads to a catalyst material, in which discrete crystalline Cu particles are partly embedded in a continuous phase comprising oxides and carbonates of at least Zn and Al, said crystalline Cu particles having a lattice constant of 3,615 A or more, preferably 3.615 to 3.621 A.
  • continuous phase comprising oxides and carbonates of at least Zn and Al
  • the molar ratio of Cu and Zn is 0.5/1 to less than 2.8/1 and the Al content is 5 to 30 3 ⁇ 4 ⁇ by mol, based on all metal constituents, and
  • the lattice constant of the crystalline Cu particles is 3.615 A or more, preferably 3.615 to
  • This catalyst material is preferably obtained by reducing the above catalyst precursor material in the presence of hydrogen .
  • precursor material comprising the steps of
  • Figure 1 shows a HRTEM picture of the catalyst material obtained in example 2.
  • Figure 2 shows a HRTEM picture of the catalyst material obtained in reference example 2.
  • Figure 3 relates to a schematic illustration of the
  • Figure 4 shows the TGA curve obtained in a thermal analysis of the uncalcined catalyst precursor material described in example 1.
  • Figure 5 shows the pore distribution of the calcined catalyst precursors according to exam le 1 and reference example 1.
  • Figure 6 shows the XRD pattern of the calcined catalyst precursor materials according to example 1 and reference example 1.
  • Figure 7 shows the TPR (temperature programmed reduction) curves of the calcined catalyst precursor materials of example 1 and reference example 1.
  • Figure 8 shows the EDX (electron dispersive X-ray ⁇ analysis of local compositions in the catalyst materials of example 2 and reference example 2.
  • Figure 9 shows the Pawley refinement of XRD patterns of the reduced catalyst materials according to example 2.
  • Figures 10 and 11 show HRTEM pictures of the calcined
  • narrower range e.g. b-c
  • narrower range also discloses the two possible part-ranges lying within the overall range on either side of the narrower range.
  • a-d further embodiments are characterized by all ranges (e.g. a-b ( a-c, b-d or c-d) which can be formed b combining any of the upper limit or the lower limit of this explicitly defined broader
  • molar contents and ratios of metal atoms refer to the average bulk composition, as can be
  • the present invention relates to a
  • Cu/Zn/Al catalyst precursor material comprising oxides and carbonates of copper, zinc and aluminum wherein copper and zinc are present together in a greater molar amount than aluminum, and wherein the standard deviation of the local molar Al content, as measured by EDX, is not more than 50%,
  • invention thus relates to a Cu/Zn/Al catalyst precursor material comprising oxides and carbonates of copper, zinc and aluminum wherein copper and zinc are present together in a greater molar amount than aluminum, and
  • the molar Cu/Zn ratio can be chosen in accordance with known catalysts. It ranges for instance from 0.2/1 to 5.5/1, or 0.4/1 to 4.0/1. It is believed that molar Cu/Zn ratios of less than 2.8/1 exert a positive influence on the formation of small crystalline Cu particles in the reduced and
  • Aluminum in particular in form of aluminum oxide, on the other hand, is regarded as thermal stabiliser for the Cu crystallites preventing them from sintering.
  • the aluminum content is preferably 1 to 30% by mol, more preferably 5 to 25 % by mol , in particular 10 to 20 % by mol, based on all metal constituents.
  • the molar ratio Cu/Zn is 0.5/1 to less than 2.8/1 (with the above further preferred ranges) and the Al content is 1 to 30 % by mol based on all metal constituents.
  • the claimed catalyst precursor material and thus also the resulting catalyst material, comprises copper, zinc and aluminum, as the only metal constituents,
  • aluminum may be partially
  • thermally stabilizing oxides such as cerium, lanthanum, zirconium, titanium, chromium, manganese or magnesium.
  • the total content of the substituting metal atom (s) is preferably not more than 15 mol % , more preferably not more than 10 mol% and even more preferably not more than 5 mol% based on all metal constituents .
  • the claimed catalyst precursor material is preferably
  • the homogenous nature of the catalyst precursor material can be described by relatively small variations in the local composition, as measured by electron dispersive X-ray
  • the standard deviation of the local molar Al content is not more than 50% , more preferably not more than 40%, more preferably not more than 30%, more preferably not more than 20% , e.g. 5 to 15%, and/or
  • the standard deviation of the local molar En content is not more than 40%, more preferably not more than 30% , more preferably not more than 20%, more preferably not more than 15%, e.g. 4 to 12% , and/or 3) the standard deviation of the local molar Cu content is not more than 25%, more preferably not more than 20%, more preferably not more than 15% , more preferably not more than 10%, e.g. 1 to 7%; each based on the average local molar content of Al , Zn or Cu as determined by EDX under the conditions described in the experimental section.
  • Condition 1 is particularly suited to characterise the preferred embodiments of the present invention and to
  • each of these three conditions may, however, be used by its own or in combination with one or two further conditions to describe further embodiments of the present invention.
  • the sample holder grid plate with a holey carrier film, for instance a holey amorphous carbon film
  • sample preparation without the use of organic solvents as dispersing agents, by adhering dry powder particles of the catalyst (precursor) material to the surface of the dry carrier film, does not lead to a sufficient number of areas for analysis of 100 local compositions, one may for instance prepare a second or further samples in the same manner ⁇ without solvent)
  • Alternative sample preparation techniques may also be used as long as they do not adversely affect the chemical composition of the sample, for instance a sample preparation by dipping the carrier into a dispersion of particles of the catalyst (precursor) material in a suitable dispersion agent ⁇ organic solvent) , if necessary in the absence of oxygen (to prevent the oxidation of active cupper particles) under use of an inert gas , followed by evaporating the organic solvent.
  • This "wet" preparation technique typically leads to greater amounts of catalyst (precursor) material per unit area of the carrier film.
  • the background signal from the carrier film material for instance carbon signal
  • the illuminated area of the TEM spectrometer is focused in 100 individual measurements on the local compositions defined by these circles. The results are averaged and the standard deviation is calculated therefrom,
  • compositions as defined above sufficiently characterize local variations in the bulk of the sample since EDX measurements show a considerable penetration depth (preferably at least 500 nm) . Moreover, the region analyzable by EDX is believed to be representative for the metal variation throughout the bulk of the entire sample.
  • the claimed catalyst precursor material shows a very low degree of crystallinity and is preferably X-ray amorphous under standard XRD
  • amorphous is to be understood as absence of “well-defined diffraction peaks” .
  • well-defined diffraction peak is to be understood as relating to a diffraction signal and an FWHM ⁇ full width at half maximum), i.e.. the width of the peak at 50% of its height above the base line, of at most 3° in 2 theta (2 ⁇ ) .
  • crystallinity display less than 20%, preferably less than 10%, more preferably less than 5% of crystalline regions as can be observed in BRTEM pictures obtained under the
  • Crystalline regions ( ypically small ZnO or CuO phases) show
  • the projected area of these crystalline regions can be determined, for instance manually, and related to the entire projected area of the catalyst precursor material observed in HRTEM .
  • low crystalline materials are characterized by the absence of crystalline areas that have a diameter of more than 20 nm, more
  • the preferred low crystallinity or X-ray amorphous nature of the claimed catalyst precursor material also indicates that discrete crystalline ZnO and AI2O3 particles or spinel phases or crystallites are preferably absent therein.
  • the carbonate content expressed as C0 2 and
  • the carbonate content is 5 wt.-% or more, preferably 10 wt . - % or more.
  • the carbonate content does not exceed 30 wt, ⁇ %.
  • the carbonate content ranges from 12 to 25 wt . - % , e.g. from 13 to 19 wt . - % , expressed as CO2 ⁇
  • These carbonate contents can be adjusted using appropriate amounts of carbonates as starting materials in combination with a calcination temperature that does not exceed 450 °C as explained further below.
  • the catalyst precursor material of the invention preferably has a BET surface, as measured with nitrogen at 77 K, of 90 m 2 /g or more, more preferably 100 m 2 /g or more, even more preferably 110 m 2 /g or more.
  • the upper limit of the BET surface area is not specifically limited, but is for instance 250 m 2 /g.
  • the claimed catalyst precursor material comprises pores with radii of 2 to 3 nm. These pores preferably account for 20 to 40%, e.g. 25 to 35% of the total porosity.
  • pores having radii of i to 10 nm account for 45 to 90 % , more preferably 55 to 80% of the total porosity and
  • Pores with radii above 100 nm are preferably absent . This preferred pore size distribution suggests that in the claimed catalyst precursor material as well as in the resulting catalyst material the homogeneous oxide/carbonate phase itself might be porous in contrast to known catalysts where pores are only or primarily present between discrete ZnO and AI2O3 particles .
  • TPR maximum rate of reduction
  • the present invention also relates to a Cu/Zn/Al catalyst material comprising discrete crystalline Cu particles partly embedded in. a continuous phase comprising oxides and
  • the lattice constant of the crystalline Cu particles is 3,615 A or more, preferably 3.615 to 3.621 A.
  • the continuous phase comprising oxides and carbonates of at least Zn and Al is in the following also referred to as
  • This catalyst material is preferably obtained by reducing the above -described catalyst precursor material. Accordingly, if not stated otherwise, features and preferred features
  • characterizing embodiments of the precursor catalyst material can also be used to describe the resulting catalyst material .
  • the molar ratio of Cu and Zn is 0.5/1 to less than 2.8/1 and the Al content is 1 to 30 % by mol based on all metal constituents.
  • the carbonate content may be lowered during the activation treatment and is for instance 1-25 wt,%, e.g. 2-22 wt.%, 3-19 wt.%, 4-16 wt . % or 5-12 wt.%, each expressed as C0 2 .
  • crystalline Cu particles constitute the active catalyst sites . They are formed during the reduction step since copper as the most noble metal is reduced first and tends to
  • the oxide/carbonate phase in the form of discrete particles .
  • These particles preferably have an approximately spherical or oval shape .
  • the diameter of individual Cu particles can be determined by measuring projected areas of individual particles in the TEM images (TEM analysis as described in the experimental section) and calculating the equivalent diameter which corresponds to the diameter of a circle with the same area . To obtain a reliable result with a low standard deviation, the total number of measured particles was 5000.
  • the average particle diameter (volume weighted) which is preferably also within the above nm ranges , can be determined in the same manner .
  • the surface of the copper particles must be accessible to the reactant gas mixture to develop its catalytic activity.
  • This property of the claimed catalyst material can also be expressed via the copper surface area (S ⁇ ) , It is preferred that the claimed catalyst material displays SQ U values of at least 10 m 2 /g, more preferably at least 15 m 2 /g, even more preferably at least 20 m 2 /g .
  • the SQ U value of 24.8 m 2 /g measured for the catalyst material of example 2 indicates for instance that about two thirds of the catalyst surface are in contact with the surrounding continuous Al/Zn phase .
  • the accessible Cu particle surface is not the only factor influencing catalytic activity. Without wishing to be bound by mechanistical considerations , it would appear that the homogenous nature (and the preferred low crystallinity) as well as the
  • the Cu particles are present in a non-equilibrium form reflected by an enlarged Cu lattice constant ⁇ the equilibrium lattice constant of bulk copper is 3.610 A).
  • the Cu lattice constant of the partly embedded Cu particles is preferably 3.615 A or more .
  • Preferred embodiments relate to lattice constants ranging from 3.615 to 3.621 A, 3.616 to 3.620 A, and 3.617 to 3.619 A.
  • the continuous Zn/Al phase shows a low degree of crystallinity or is preferably X-ray amorphous .
  • X-ray amorphous is to be understood in the above-explained sense as free of well-defined diff action peaks .
  • the net area of the diffraction signal in the range 30.0- 39.0° 2theta (region of 100, 002, 101 reflections of ZnO) should be lower than 20%, preferably lower than 15% of the net area of the diffraction signal in the range 39.0-47.0° 2theta (region of 111 reflection of Cu) .
  • Net area is to be understood as the area defined by the measured diffraction signal curve and the linear background in the given angular range.
  • Linear background is to be understood as a straight line between the measured intensity at the lower limit of the given angular range and the measured intensity at the upper limit of the given angular range.
  • the preferred low crystallinity or X-ray amorphous nature of the continuous Zn/Al phase also indicates that discrete crystalline ZnO and AI2O3 particles or spinel phases or crystallites are preferably absent therein.
  • the catalyst material of the invention can be used as
  • shaped catalyst precursor bodies of a definite size are formed from the catalyst precursor material followed by reduction in the presence of hydrogen under the conditions explained below. This reduction can be achieved for instance by contacting the precursor bodies with synthesis gas , pure hydrogen or hydrogen gas diluted with inert gas . It is preferred to add a lubricant, for instance graphite, in small amounts, for instance 1 to 5 wt . -%, based on the final weight of the catalyst (precursor) .
  • a lubricant for instance graphite
  • the size of the catalyst (precursor) bodies to be used. The following structural features are however preferred.
  • the macroscopic size (average longest diameter) of the individual catalyst (precursor) bodies preferably ranges from
  • Catalyst bodies of this size can be obtained by processes known in the art, for instance by pressing a dried calcined catalyst precursor material, newly crushing the pressed material and carrying out size- selecting steps such as sieving, before conducting the activation
  • the catalyst precursor material is coated onto a carrier according to techniques known in the art prior to the reduction step.
  • This coating of a carrier with the respective catalyst precursor materials can be equally effected at an earlier stage, for instance prior to the calcination treatment.
  • the carrier which is preferably inert, can have any shape and surface structure . However, regularly shaped,
  • the size and shape of the carrier bodies is determined, for example, by the dimensions , primarily the internal diameter of the reaction tubes if the catalyst is used in tube or tube-bundle reactors .
  • the diameter of the carrier body should then be between 1/2 and 1/10 of the internal diameter of the reactor .
  • the carrier dimensions are determined, for example, by the fluid dynamics in the reactor. Suitable materials are, for example .
  • the proportion of the layer of catalyst precursor material applied to the carrier is preferably 1 to 30% by weight, particularly preferred 2 to 20% by weight based on the total mass of the final carried catalyst material.
  • the thickness of the catalyst material layer is preferably 5 to 300 jjm, particularly preferred 5 to 10 pm.
  • the claimed catalyst precursor material is preferably produced in a process comprising the following steps .
  • step (d) and (e) and/or step (e) and (f) it is preferred to conduct at least one washing step between steps (d) and (e) and/or step (e) and (f) , respectively, If the dried recovered solid obtained in step (e) is subjected to a washing step, it is preferred to newly dry the washed solid before subjecting the same to the final calcination step.
  • the first and second solutions described above may be mixed in any manner or order .
  • the first solution can be added to the second solution, or the second solution can be added to the first solution, or a mixture of the two solutions can be obtained by simultaneously mixing the two solutions such as by simultaneously adding the two solutions to a vessel . It is desirable that the mixing of the first and second
  • step (c) be conducted at a pH above about 5.5 (e.g. pH 5.5 to 9) , and more generally above about 6.0, e.g. at a pH of 6.0 to 7.0.
  • a pH above about 5.5 e.g. pH 5.5 to 9
  • 6.0 e.g. at a pH of 6.0 to 7.0
  • the pH of the resulting mixture can be controlled by varying the rate of addition of the second solution which contains an alkaline material . As the rate of addition of the second solution increases , the pH of the resulting mixture increases .
  • the water-soluble copper and zinc salts utilized to form the first solution are copper and zinc salts such as nitrates, acetates, sulfates , chlorides , etc . It is presently
  • any water-soluble aluminum salt can be utilized to prepare the second solution, and the aluminum salt generally is a basic aluminum salt such as sodium aluminate .
  • Alumina gels can also be utilized even though, according to one preferred embodiment of the
  • Al oxide present in the continuous Zn/Al phase is nei her obtained from an aluminum hydroxide sol or gel nor from colloidally dispersed AI2O3.
  • the second solution also contains at least one alkaline carbonate -containing water-soluble material such as such as sodium carbonate or ammonium carbonate .
  • the carbonate- containing salt may be used in combination with other water- soluble salts such as sodium hydroxide or ammonium hydroxide .
  • the pH of the mixture obtained by mixing the first and second solutions should be within the range of from about 5.5 to about 9.0 and more preferably is at least 6 , and most preferably at least about 6,0 to 7.0. As noted above , the pH of the mixture can be maintained as desired by adj sting the relative addition rates of the two solutions . Additionally, the mixture
  • the obtained from the first and second solutions is preferably maintained at a temperature of from about 50-80°C (however preferably not over extended periods of time in order to suppress aging processes as explained below) ,
  • a precipitate is formed and recovered by techniques well known in the art such as by filtration, centrifugation, etc .
  • the recovered precipitate preferably is washed with water to remove
  • drying is effected by continuous spray drying. During spray drying the recovered insoluble solid is exposed to temperatures ranging preferably from 80 to 220°C.
  • the spray dryer typically works with at least two temperature zones within this range which preferably include an inlet temperature higher than the temperature at the outlet. Spray drying may for instance be effected with an inlet temperature of 180 ⁇ to 220°C and an outlet temperature of 80 to 120 °C, Preferably, spray drying is conducted continuously.
  • the present inventors have found that it is preferred to suppress aging processes in the manufacture of the catalyst
  • a second spray drying step may follow.
  • the time period between the formation of the insoluble solid in step (c) and the recovery (step (d) ) is shorter than Ih, preferably shorter than 50 min, more preferably shorter than 40min, for instance shorter than 30 min, e.g. 20 min or less. Aging processes can be recognized via colour changes of the insoluble solid being in contact with the mother liquid.
  • the calcination (step f) is preferably conducted in an oxygen-containing atmosphere at a temperature of 200-400°C, preferably 280-380°C, more preferably 310-350°C.
  • this calcination reaction is usually conducted at atmospheric pressure. In principle it is, however, also possible to conduct this step under
  • oxygen-containing atmosphere air or a synthetic oxygen-containing atmosphere can be used. Depending on the other process conditions, oxygen is normally not employed in contents of more than 50 vol . - % . Suitable oxygen volume ratios are for instance 1 to 40 vol . % , 5 to 35 vol . - or 10 to 30 vol . -% . The remainder is nitrogen as in air or any other inert gas such as Ar or He.
  • the calcined catalyst precursor material obtained in step (f ) can be activated by reduction in the presence of hydrogen. This reduction is achieved by contacting the calcined
  • catalyst material with a hydrogen-containing atmosphere such as synthesis gas, pure hydrogen or hydrogen diluted with an inert gas ⁇ e.g. nitrogen, helium or argon) .
  • a catalyst material as claimed arises by the segregation of crystalline Cu particles from the surrounding
  • the reduction step is conducted under conditions known in the art, preferably at a temperature of from 150 to 300°C, more preferably 175 to 270°C and
  • the reduction is performed by- heating the catalyst precursor material in an atmosphere comprising 1 to 10 vol . - % hydrogen, preferably 2-7 vol . - % hydrogen, the remainder being an inert gas, such as nitrogen, argon or helium, to a temperature of 230 to 260°C.
  • the heating rate is preferably 1-5 K/min and the precursor material is held at the final temperature preferably for at least 15 minutes , for instance 30 minutes or more .
  • the precursor material is heated to 150 to 200°C at a rate of 0.5 to 5 K/min in a gas mixture comprising 1 to 5 vol. -% hydrogen, the remainder being inert gas, such as nitrogen or helium, followed by reduction in 100% hydrogen at a higher temperature of
  • precursor material is preferably held at the final
  • the catalyst of the invention (and thus also the catalyst material comprised therein) can be used under conventional conditions to prepare methanol from synthesis gas, that is a technical mixture of hydrogen, carbon monoxide and carbon dioxide .
  • an inert gas such as 3 ⁇ 4 or helium in an amount of
  • the reaction is conducted at a pressure of 10 to 150 bar, preferably 20 to 70 bar, more preferably 35 to 55 bar ⁇ each absolute pressure values) , and at a temperature of preferably 200 to 300°C over the catalyst (material) of the present invention.
  • the space velocity may be about 1000 to 50000, for instance 5000 to 30000 1 synthesis gas mixture per hour and 1 catalyst
  • TGA-EGA Thermogravimetric analysis-evolved gas analysis
  • TG curves of the hydroxy carbonate precursors were recorded on a Netzsch STA 449-C thermoba1ance with an attached quadrupol mass spectrometer for EGA (Pfeiffer Omnistar) .
  • a heating rate of 2 K/min was applied in synthetic air.
  • TPR Temperature programmed reduction
  • TPR was performed by raising the temperature to 250 °C in a fixed bed reactor (CE instruments TPDRO 1100) with a heating rate of 2 K/min. H 2 consumption was monitored using a thermal conductivity detector,
  • TPR studies were conducted with 50 mg of calcined catalyst precursor material (powder) in an atmosphere of 5% hydrogen and 95% helium at a flow rate of 80ml/min.
  • Nitrogen adsorption-desorption isotherm is measured at 77 K using for example an Autosorb- 1 instrument ⁇ Quantachrome ) .
  • the sample Prior to the adsorption, the sample is outgassed in vacuum at 353 K for 4 h.
  • Calculation of the pore size distribution is performed using the desorption branch of the isotherm and the Barrett-Joyner-Halenda (BJH) method, as described in E . P . Barrett , L.G. Joyner, P.P. Halenda, J. Amer . Chem. Soc . 73 (1951) 373.
  • Full adsorption/desorption isotherms in the p/ o range 0.001 to 1 were recorded .
  • the Quantachrome AUTOSORB software was used to calculate the pore size distribution based on the complete desorption branch of the isotherm and the Barret-Joyner-Halenda (BJH) method.
  • the sample size is around 0.1 g .
  • the copper surface area was determined applying N 2 0 reactive frontal chromatography with 1 vol . -% 2O in he1ium according to the method proposed by Chinchen et al . (G. C . Chinchen, C. M. Hay, H. D. Vanderwell, K. C. Waugh, J. Catal . 1987, 103, 79) at somewhat more moderate reaction conditions (O. Hinrichsen, T. Genger, M. Muhler, Chem. Eng. Technol . 2000, 11, 956-959) .
  • XRD XRD
  • XRD patterns of the samples of catalyst precursor materials were collected on a Stoe Stadi-p diffractometer equipped with a primary focusing Ge monochromator and a linear position sensitive detector (resolution 0.005 0 /channel , step size 0.1° ) in the 2 ⁇ range 4-80° with a counting time of 10s using Cu Ka radiation in transmission geometry.
  • the coefficient of spherical aberration was C s 1,35 mm.
  • High- resolution images with a pixel size of 0.016 nm were taken at the magnification of 1083000x with a CCD camera.
  • the EDAX software ⁇ Genesis 5.21) was used for EDX raw data analysis.
  • the theoretical k factors implemented into Genesis 5.21 were used.
  • the precipitate was aged for 3 h in the mother liquor . During aging the colour changed from light blue to green which indicates the formation of zincian malachite or rosasite and hydrotalcite-like phases.
  • the sample was thoroughly washed with water, dried and calcined ( 3h, 330°C, 2 K/min) in static air.
  • the N2 adsorption/desorption isotherm of the calcined precursor material B (Reference Example 1) showed a hysteresis indicating capillary condensation in the pores .
  • the surface area was determined to be 88 m 2 /g .
  • the calcined precursor material of Reference Example 1 was reduced in 5% 3 ⁇ 4 (heating to 250°C at 2 K/min followed by 0.5 h at 250°C, flow rate 80 ml/min) in a fixed bed reactor- ⁇ TPDRO 1100, CE instruments) to obtain a catalyst material showing activity in the synthesis of methanol from synthesis gas.
  • phase (i) Cu particles of an average diameter ⁇ 10 nm were observed to be separated by small ZnO particles preventing them from sintering and forming a porous framework of individual particles . These areas of the catalyst were commonly observed and exhibited Cu-rich compositions near the nominal metal ratio.
  • Phase (iii) presumably developed from an amorphous aluminum hydroxide precursor phase , which was not detected by XRD .
  • the accessible copper surface SQ U was determined by 3 ⁇ 40 chemisorption to be 36.1 + 1 m 2 /g .
  • the continuously prepared precursor A was precipitated from a Cu, Zn nitrate solution ("first solution", 0,85 M) of the same Cu: Zn ratio as in Sample B (Reference example 1),
  • the "first solution” was prepared by dissolving 87,0 g
  • the "second solution” was prepared by using 600ml of a 1.6 M Na 2 C0 3 solution as precipitating agent to which 9.8g aluminate ⁇ a2 l20 x 3H 2 0) solution was added under stirring .
  • An automatic lab reactor ⁇ Labmax, Metier-Toledo was filled with 400 ml water and preheated to 65°C. Over a time period of 45 minutes, 600 ml of the above copper zinc nitrate solution were added while the above aluminate carbonate
  • the pump rate was such (about 35 ml/min) that the filling level in the reactor did not change .
  • the granulate obtained at the outlet of the spray-dryer was repeatedly slurried in water, stirred over 5min and filtrated off until the conductivity of the filtrate was less than 0.5 mS/cm (typically after the 5 th repeat) .
  • the solid wet filtration residue was slurried in about 11 of water and spray-dried under the same conditions as stated above.
  • the dried material is calcined (3h, 330°C, 2 K/min) in static air.
  • the uncalcined material was also subj ected to a TGA analysis as shown in Figure 4 which revealed the following.
  • Up to ca . 300 °C the uncalcined catalyst precursor material decomposed in an ill-defined dehydroxlation step with almost linear mass loss mostly due to H 2 0 emission. Only minor C0 2 emission is observed before a temperature around 463 °C and, hence , most of the carbonate persist the calcination treatment at a temperature of 330°C .
  • the decarbo 1yation step contributes 13% to the overall mass loss of 30.5 % at 600°C (C0 2 content of claimed sample about 15.8%) .
  • XRD patterns of the calcined material showed only broad and weak reflections at the positions where peaks of CuO (ICDD 80-76) are expected . Characteristic peaks for Zn or Al compounds could not be observed .
  • the continuous Zn/Al phase wherein the CuO particles are partly embedded can thus be considered as X-ray amorphous .
  • the 2 adsorption/desorption isotherms of the calcined intermediates of catalyst A was also of type V indicating the presence of mesopores .
  • the surface area was determined to 114 m 2 /g.
  • the pore size distribution of the calcined sample was determined using the BJH method and desorption data and is shown in Figure 5 ("catalyst A" ) .
  • Catalyst A A maximum around 20 nm is observed and assigned to inter-particle pores though in a relatively low abundance when compared with a second type of pores with radii of 2-3 nm. These small pores contribute considerably to the surface area suggesting that in catalyst A the oxide matrix itself might be porous.
  • the calcined sample was also subjected to a TPR analysis which gave the results shown in Figure 7 for "catalyst A" .
  • the maximum of the TPR curve was at 18 7 ° C . Shoulders of the TPR profile of catalyst B (Reference Example 1) at the high and low temperature side are more pronounced compared to catalyst A confirming the lower degree of homogeneity. The maximum rate of reduction is observed at a significantly higher temperature for catalyst A indicating stronger metal- oxide interactions in agreement with the previously described microstrueture model.
  • the catalyst structure was investigated by HRTEM analysis as shown in Figure 1.
  • the microstrueture of the catalyst material obtained in Example 2 was very homogeneous and no different types of materials were observed by TEM.
  • Cu particles were nearly spherically shaped (Fig. 1) .
  • Fig. 1 Unlike catalyst B ⁇ Reference Example 2) , individual separated oxide particles are hardly observed and, consequently, the porous Cu/ZnO particle arrangement is absent in the new material.
  • the Cu particles are partly embedded in the oxide matrix resulting in an arrangement that resembles a supported system with an intimate interface contact of metal particles and contiguous Cu depleted oxide.
  • a statistically meaningful Cu particle size distribution was determined for both samples by measuring projected areas in TEM images of 16308 and 9930 particles for catalyst A and B, respectively.
  • the local compositions shown in Fig . 8 were determined on 16 clusters of primary catalyst particles which had a total projected area of partially more than 500 nm x 500 nm .
  • the local metal contents and local compositions were thus analyzed in a slightly different way than previously described and defined . It is believed that this difference has no impact on the assessment of the homogenity of the samples .
  • the corresponding standard deviation calculated from 13 local compositions of the catalyst material of reference example 2 was much bigger, that is more than 100% for the local Al content, about 28% for the local Cu content and about 14% for the local Zn content .
  • the accessible copper surface SQ U was determined by 3 ⁇ 40 chemisorption to be 24.8 + 1.2 m 2 /g .
  • XRD data further confirmed that the Cu particles were in a non-equilibrium state, which is reflected by an enlarged Cu lattice constant. It was determined to be 3.618 ⁇ 0.001 A by fitting of XRD data ⁇ Fig. 3) . This value is far removed from the value of bulk copper (3. SloA) . It can be speculated that the Cu lattice is distorted by enhanced metal/oxide interactions such as epitaxial stress at the interface or partial dissolution of zinc or oxygen in the Cu lattice across the interface leading to high intrinsic activity.
  • Catalytic testing was performed in a flow set-up equivalent to that described by O. Hinrichsen, T. Genger , M. Muhler , Chew. Eng. Technol, 2000, 11, 956-359.
  • a calibrated quadrupole mass spectrometer (Pfeiffer Vacuum, Thermostar) was used.
  • a glass-lined stainless steel microreactor was filled with 100 mg catalyst (sieve fraction 250-355 ⁇ ) .
  • the catalyst precursor materials A (Example 2 ) and B (Reference Example 2), respectively, were reduced as follows: (i) by heating in a gas mixture of 2.0 % H 2 /He to 175 °C (at 1 K min "1 ) followed by holding the material at 175 °C over 15h and (ii) subsequently heating in 100% H 2 to 240 °C (at 1 K min "1 ) followed by holding the material at 240°C over 30 min.
  • the "initial activity" of the catalyst under steady-state conditions was determined at 220°C and at 10 bar pressure, using a flow rate of 50 N mi min "1 .
  • the catalyst was cooled down in the feed at atmospheric pressure. Overnight, the catalyst was heated in the feed (at atmospheric pressure) to 513 K (240°C) at a very slow heating rate (0.5 K/min, i.e. quasi stationary).
  • the methanol production is determined by the thermodynamic equilibrium, so that the theoretical concentration can be calculated and compared to the measured value. In this way, the calibration of the MS can be double checked. This overnight procedure at

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WO2015070298A1 (pt) * 2013-11-12 2015-05-21 Petróleo Brasileiro S.A. - Petrobras Catalisador para processo de reforma à vapor a baixa temperatura
CN106132542A (zh) * 2014-03-26 2016-11-16 科莱恩国际有限公司 加氢催化剂及其制备方法
US10035137B2 (en) 2012-09-28 2018-07-31 Clariant International Ltd. Hydrogenation catalyst and process for production thereof by the use of uncalcined starting material
US10087355B2 (en) 2016-03-17 2018-10-02 Saudi Arabian Oil Company Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier
US10105684B2 (en) 2016-03-17 2018-10-23 Saudi Arabian Oil Company Synthesis of transition-metal adamantane salts and oxide nanocomposites, and systems and methods including the salts or the nanocomposites
US10106482B2 (en) 2016-03-17 2018-10-23 Saudi Arabian Oil Company Synthesis of magnesium adamantane salts and magnesium oxide nanocomposites, and systems and methods including the salts or the nanocomposites
US10138199B2 (en) 2016-03-17 2018-11-27 Saudi Arabian Oil Company High aspect ratio layered double hydroxide materials and methods for preparation thereof
US10252245B2 (en) 2016-03-17 2019-04-09 Saudi Arabian Oil Company High temperature layered mixed-metal oxide materials with enhanced stability
US10875092B2 (en) 2017-05-19 2020-12-29 Saudi Arabian Oil Company Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites
US10906028B2 (en) 2017-05-19 2021-02-02 Saudi Arabian Oil Company Synthesis of transition-metal adamantane salts and oxide nanocomposites, and systems and methods including the salts or the nanocomposites
US11000833B2 (en) 2016-12-15 2021-05-11 Clariant International Ltd Tableted catalyst for methanol synthesis having increased mechanical stability
WO2022112328A1 (en) * 2020-11-24 2022-06-02 Topsoe A/S Process and catalyst for the catalytic hydrogenation of organic carbonyl compounds
CN114660256A (zh) * 2022-04-02 2022-06-24 昆明理工大学 一种铜锌催化剂中各价态铜含量的测定方法
US11603342B2 (en) 2016-02-16 2023-03-14 Fundació Institut Cat Alá Dinvestigació Química (Iciq) Methanol production process
US11993519B2 (en) 2017-03-06 2024-05-28 Oxford University Innovation Limited Layered double hydroxide precursor, their preparation process and catalysts prepared therefrom

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CN116848065A (zh) * 2022-01-14 2023-10-03 世拓拉斯控股公司 含锌水滑石

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US10035137B2 (en) 2012-09-28 2018-07-31 Clariant International Ltd. Hydrogenation catalyst and process for production thereof by the use of uncalcined starting material
WO2015070298A1 (pt) * 2013-11-12 2015-05-21 Petróleo Brasileiro S.A. - Petrobras Catalisador para processo de reforma à vapor a baixa temperatura
US10226760B2 (en) 2014-03-26 2019-03-12 Clariant International Ltd. Hydrogenation catalyst and method for producing same
CN106132542A (zh) * 2014-03-26 2016-11-16 科莱恩国际有限公司 加氢催化剂及其制备方法
US11603342B2 (en) 2016-02-16 2023-03-14 Fundació Institut Cat Alá Dinvestigació Química (Iciq) Methanol production process
US10252245B2 (en) 2016-03-17 2019-04-09 Saudi Arabian Oil Company High temperature layered mixed-metal oxide materials with enhanced stability
US10087355B2 (en) 2016-03-17 2018-10-02 Saudi Arabian Oil Company Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier
US10106482B2 (en) 2016-03-17 2018-10-23 Saudi Arabian Oil Company Synthesis of magnesium adamantane salts and magnesium oxide nanocomposites, and systems and methods including the salts or the nanocomposites
US10105684B2 (en) 2016-03-17 2018-10-23 Saudi Arabian Oil Company Synthesis of transition-metal adamantane salts and oxide nanocomposites, and systems and methods including the salts or the nanocomposites
US10138199B2 (en) 2016-03-17 2018-11-27 Saudi Arabian Oil Company High aspect ratio layered double hydroxide materials and methods for preparation thereof
US10906859B2 (en) 2016-03-17 2021-02-02 Saudi Arabian Oil Company Adamantane-intercalated layered double hydroxide
US11000833B2 (en) 2016-12-15 2021-05-11 Clariant International Ltd Tableted catalyst for methanol synthesis having increased mechanical stability
US11993519B2 (en) 2017-03-06 2024-05-28 Oxford University Innovation Limited Layered double hydroxide precursor, their preparation process and catalysts prepared therefrom
US10875092B2 (en) 2017-05-19 2020-12-29 Saudi Arabian Oil Company Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites
US11351604B2 (en) 2017-05-19 2022-06-07 Saudi Arabian Oil Company Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites
US10906028B2 (en) 2017-05-19 2021-02-02 Saudi Arabian Oil Company Synthesis of transition-metal adamantane salts and oxide nanocomposites, and systems and methods including the salts or the nanocomposites
WO2022112328A1 (en) * 2020-11-24 2022-06-02 Topsoe A/S Process and catalyst for the catalytic hydrogenation of organic carbonyl compounds
CN114660256A (zh) * 2022-04-02 2022-06-24 昆明理工大学 一种铜锌催化剂中各价态铜含量的测定方法
CN114660256B (zh) * 2022-04-02 2024-01-05 昆明理工大学 一种铜锌催化剂中各价态铜含量的测定方法

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