EP3554690A1 - Catalyseur sous forme de comprimé pour la synthèse de méthanol présentant une stabilité mécanique accrue - Google Patents

Catalyseur sous forme de comprimé pour la synthèse de méthanol présentant une stabilité mécanique accrue

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Publication number
EP3554690A1
EP3554690A1 EP17842317.4A EP17842317A EP3554690A1 EP 3554690 A1 EP3554690 A1 EP 3554690A1 EP 17842317 A EP17842317 A EP 17842317A EP 3554690 A1 EP3554690 A1 EP 3554690A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
calcium aluminate
range
mixture
zinc
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17842317.4A
Other languages
German (de)
English (en)
Inventor
Sebastian Werner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant International Ltd
Original Assignee
Clariant International Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP3554690A1 publication Critical patent/EP3554690A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J19/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/30Loose or shaped packing elements, e.g. Raschig rings or Berl saddles, for pouring into the apparatus for mass or heat transfer
    • 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
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/63Pore volume
    • B01J35/633Pore volume less than 0.5 ml/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
    • B01J35/64Pore diameter
    • B01J35/6472-50 nm
    • 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
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018Addition 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)
    • 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
    • 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
    • B01J37/08Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/302Basic shape of the elements
    • B01J2219/30207Sphere
    • B01J2219/30211Egg, ovoid or ellipse
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/302Basic shape of the elements
    • B01J2219/30219Disk
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/304Composition or microstructure of the elements
    • B01J2219/30408Metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/304Composition or microstructure of the elements
    • B01J2219/30416Ceramic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/304Composition or microstructure of the elements
    • B01J2219/30475Composition or microstructure of the elements comprising catalytically active material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30Details relating to random packing elements
    • B01J2219/318Manufacturing aspects
    • B01J2219/3185Pressing
    • 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
    • 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
    • B01J2523/10Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17Copper
    • 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
    • B01J2523/20Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27Zinc
    • 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
    • B01J2523/30Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31Aluminium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00Protection of catalysts, e.g. by coating
    • 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
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    • 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
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04Mixing
    • 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

  • Suitable catalysts are systems based on copper and zinc. These are usually in the form of tablets, extrudates or granules.
  • No. 7,084,312 describes the preparation of catalysts based on copper, zinc and aluminum, for which an oxidic mixture of copper, zinc and aluminum with metallic copper, a cement or a mixture of both materials mixed and formed into tablets.
  • the catalyst is used for the hydrogenation of organic
  • the Caiciumaluminat can be subjected to a thermal treatment (calcination) before use as a binder material. This takes place at a temperature between 100 and 500 ° C, preferably between 150 and 400 ° C and more preferably between 200 and 300 ° C instead.
  • the catalysts prepared by the process according to the invention in tablet form have a lateral compressive strength of 50 to 300 N, preferably 100 to 250 N, particularly preferably 150 to 250 N in the oxide state.
  • the tablets produced by tabletting have a diameter in the range of 5 to 7 mm, a height in the range of 3 to 5 mm and a lateral compressive strength in the range of 160 to 220 N.
  • Hydrogen-nitrogen mixture is typically in the range of 1 to 4% by volume.
  • the reduction takes place, for example, at a temperature in the range from 150 ° C. to 450 ° C., in particular in the range from 180 ° C. to 300 ° C., preferably in the range from 190 ° C. to 290 ° C., particularly preferably at approximately 250 ° C.
  • Hexadecane 2-ethyl-hexanol, propylene glycol and mixtures thereof, especially iso-decanol.
  • a thin oxide layer having a thickness of, for example, 0.5 to 50 nm, preferably 1 to 20 nm, more preferably 1 to 10 nm at the surface of the Catalyst is formed which protects the shaped catalyst body from further oxidation.
  • Reduction may occur ex situ or in situ in the reaction plant in which the
  • the active copper surface of the reduced shaped catalyst body is between 20 m 2 / g and 50 m 2 / g, preferably between 20 m 2 / g and 40 m 2 / g, particularly preferably between 25 m 2 / g and 36 m 2 / g ,
  • the catalyst obtainable by the process according to the invention preferably has a BET surface area in the range from 70 to 150 m 2 / g, in particular from 75 to 140 m 2 / g and particularly preferably from 80 to 120 m 2 / g.
  • the pore volume of the shaped catalyst body according to the invention is between 150 mm 3 / g and 400 mm 3 / g, preferably between 250 mm 3 / g and 350 mm 3 / g, particularly preferably between 300 and 350 mm 3 / g.
  • the proportion of the pore volume of the pores with a radius of 7.0 to 40.0 nm of the shaped catalyst body according to the invention is between 50 and 95%, preferably between 80 and 90% of the total pore volume.
  • the invention also provides the use of the invention
  • Typical reaction temperatures of the methanol synthesis are between 200 and 300 ° C, preferably between 210 to 280 ° C, the pressure is usually in a range of 40 to 150 bar, preferably from 60 to 100 bar, and the space velocity of
  • Gas composition is in the range of 2000 to 22000 h ⁇ 1 .
  • Room velocity is the quotient of the volume flow of the synthesis gas and the volume of the catalyst in the case of a catalyst bed, the bulk volume of this bed, to understand per hour.
  • Catalyst body was a certain amount under reducing gas (2% by volume of H 2 in N 2 ) heated to 200 ° C and reduced at this temperature for 24 h. The material was cooled to room temperature under a stream of nitrogen. After that was the
  • Nitrogen stream dosed synthetic air and passivated the material. Thereafter, for the thus treated samples, their lateral compressive strength was determined as described in the previous paragraph.
  • the determination of the breaking strength was carried out by adding 100g of the
  • Diameter of 60 mm and a length of 3 m were dropped. After passing through the steel tube, the tablets were collected in a beaker.
  • the fracture fraction can be determined as the difference between the tablets used and the tablets which have withstood the dropping process without flaking, the formation of break edges or other deviations from the original cylindrical shape, divided by the weight of the tablets used.
  • the BET specific surface areas were determined by means of nitrogen adsorption according to DIN 66131.
  • the proportion by weight of calcium aluminate in the shaped catalyst body could by means of
  • X-ray diffractometry can be determined.
  • the sample was measured over a range of 5 to 90 2 ° ⁇ (step sequence 0.020 2 ° ⁇ , 1.5 sec. Measuring time per step). CuKa radiation was used.
  • the obtained spectrum of the reflection intensities was quantitatively analyzed by Rietveld refinement and the proportion of calcium aluminate in the sample certainly.
  • the TOPAS software from BRUKER was used.
  • the Cu surface was determined by first mortaring a shaped catalyst body and introducing about 100 mg of the sieve fraction of 100-250 ⁇ m into a quartz glass reactor. Subsequently, the catalyst was reduced / activated at normal pressure as described above. After completion of the reduction of the catalyst under He was heated to 35 ° C. In the exhaust stream of the reactor was a calibrated mass spectrometer, which was aligned for the detection of N 2 0 and N 2 . Now one became
  • the consumption in N 2 0 in mol could be determined. Assuming a specific copper surface area of 1 .47 10 19 atoms Cu / m 2 , a calculation of the surface was possible, the Cu surface was thus determined as the quotient of the surface and the weighed sample.
  • a 14% strength by weight aqueous sodium carbonate solution was prepared and heated to 50.degree.
  • 120 g of zinc oxide and 260 g of aluminum nitrate in 900 g of water and 270 g of 68 wt .-% HN0 3 was dissolved at 50 ° C.
  • the nitrate solution and the soda solution were combined at a temperature of 65 ° C simultaneously while maintaining the pH of 6.5 (precipitation).
  • the suspension was continuously pumped from the precipitation vessel into an aging vessel. After completion of the precipitation, the suspension was aged for at least 120 minutes at 70 ° C. The color changed from light blue (onset of aging) to green (end of aging). After aging, the suspension was filtered and the filter cake was washed until the sodium content of the filter cake, as determined by atomic absorption spectroscopy, was less than 350 ppm.
  • the filter cake was made by adding water
  • Catalyst precursor thermally treated at 330 ° C for 2 h.
  • the chemical composition was (in% by weight): 64.0% CuO, 27.8% ZnO, 8.2% Al 2 0 3 , based on the
  • the dried powder was then thermally treated at 320 ° C for 2 hours and served as the starting material for the tabletting examples.
  • Comparative Catalyst A was prepared by mixing 500 g of the catalyst powder with 2 g of graphite and then forming into tablets measuring 6 mm in diameter and 4 mm in height.
  • 500 g of the catalyst powder were mixed with 50 g of Caiciumaluminat (type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus tableted sample was not subjected to any thermal treatment.
  • Caiciumaluminat type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3
  • 500 g of the catalyst powder were mixed with 50 g of Caiciumaluminat (type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
  • Caiciumaluminat type SECAR 71, 30 wt .-% CaO, 70 wt .-% Al 2 0 3
  • the catalyst powder 500 g were mixed with 62.5 g of Caiciumaluminat (type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
  • Caiciumaluminat type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3
  • 500 g of the catalyst powder were mixed with 100 g of Caiciumaluminat (type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3 ) and 10 g of graphite. Subsequently, the mixture was molded into tablets having dimensions of 6 mm in diameter and 4 mm in height. The thus-tableted sample was then thermally treated at 400 ° C for 2 hours.
  • Caiciumaluminat type SECAR 71, 30% by weight of CaO, 70 wt .-% Al 2 0 3

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

Abstract

La présente invention concerne un catalyseur amélioré à base d'un corps moulé de catalyseur sous forme de comprimé, contenant un mélange contenant du métal, notamment du cuivre, du zinc et de l'aluminium, et de l'aluminate de calcium comme liant, la proportion en poids d'aluminate de calcium étant comprise entre 1,0 % et 30,0 %, pour la synthèse de méthanol à partir de gaz de synthèse. La présente invention concerne en outre la fabrication de ce catalyseur, ainsi que son utilisation pour la synthèse de méthanol à partir de gaz de synthèse.
EP17842317.4A 2016-12-15 2017-12-14 Catalyseur sous forme de comprimé pour la synthèse de méthanol présentant une stabilité mécanique accrue Withdrawn EP3554690A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016225171.6A DE102016225171A1 (de) 2016-12-15 2016-12-15 Tablettierter Katalysator für die Methanolsynthese mit erhöhter mechanischer Stabilität
PCT/EP2017/082815 WO2018109083A1 (fr) 2016-12-15 2017-12-14 Catalyseur sous forme de comprimé pour la synthèse de méthanol présentant une stabilité mécanique accrue

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WO2018109083A1 (fr) 2018-06-21
US11000833B2 (en) 2021-05-11
DE102016225171A1 (de) 2018-06-21
CN110072614A (zh) 2019-07-30
US20200001278A1 (en) 2020-01-02

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