WO2025002974A1 - Catalyseur d'hydrogénation pour la fabrication de peroxyde d'hydrogène - Google Patents

Catalyseur d'hydrogénation pour la fabrication de peroxyde d'hydrogène Download PDF

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WO2025002974A1
WO2025002974A1 PCT/EP2024/067243 EP2024067243W WO2025002974A1 WO 2025002974 A1 WO2025002974 A1 WO 2025002974A1 EP 2024067243 W EP2024067243 W EP 2024067243W WO 2025002974 A1 WO2025002974 A1 WO 2025002974A1
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catalyst
metal
process according
amorphous
support
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Jolien DE WAELE
Martin Bousmanne
Francois Dabeux
Christophe RIEZ
Pascal VANDENBUSSCHE
Andrew WILLSON
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Solvay SA
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Solvay SA
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Priority to CN202480043190.7A priority Critical patent/CN121463995A/zh
Priority to EP24735610.8A priority patent/EP4731334A1/fr
Publication of WO2025002974A1 publication Critical patent/WO2025002974A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/022—Preparation from organic compounds
    • C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
    • 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
    • B01J21/12—Silica and 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing

Definitions

  • the present invention relates to an anthraquinone process (AO) for the manufacture of hydrogen peroxide, wherein the hydrogenation step is conducted with the aid of a catalyst comprising in addition to palladium (Pd) at least one other metal, and an amorphous catalyst support.
  • AO anthraquinone process
  • Hydrogen peroxide is one of the most important inorganic chemicals to be produced worldwide. Its industrial applications include textile, pulp and paper bleaching, organic synthesis (propylene oxide), the manufacture of inorganic chemicals and detergents, environmental and other applications.
  • Synthesis of hydrogen peroxide is predominantly achieved by using the Riedl-Pfleiderer process (originally disclosed in U.S. Pat. Nos. 2,158,525 and 2,215,883), also called anthraquinone loop process or AO (auto-oxidation) process.
  • Riedl-Pfleiderer process originally disclosed in U.S. Pat. Nos. 2,158,525 and 2,215,883
  • AO auto-oxidation
  • This well-known cyclic process makes use typically of the auto-oxidation of at least one alkylanthrahydroquinone and/or of at least one tetrahydroalkylanthrahydroquinone, most often 2-alkylanthrahydroquinone, to the corresponding alkylanthraquinone and/or tetrahydroalkylanthraquinone, which results in the production of hydrogen peroxide.
  • the first step of the AO process is the reduction of the chosen quinone (alkylanthraquinone or tetrahydroalkylanthraquinone) into the corresponding hydroquinone (alkylanthrahydroquinone or tetrahydroalkylanthrahydroquinone) using hydrogen gas from any source and a catalyst in an organic solvent (generally a mixture of solvents).
  • the catalyst used in the reduction step of the AO-process is usually a metal-based catalyst having a sufficient activity and selectivity to reduce the chosen quinone to the corresponding hydroquinone, e.g., 2-alklyanthraquinone to 2-alkyl-9,10-anthrahydroquinone.
  • the invention relates to an anthraquinone process (AO) for the manufacture of hydrogen peroxide, wherein the hydrogenation step is carried out with a catalyst in the form of catalyst powder particles having a mean particle size between 100 pm and 200 pm, used in a slurry, and wherein the catalyst comprises palladium (Pd), at least one other metal, and an amorphous catalyst support comprising silicon dioxide and alumina (SiAlOx) in an aerogel -physical form, wherein the alumina is incorporated into the silicon dioxide structure at the molecular level.
  • AO anthraquinone process
  • a compound means one compound or more than one compound.
  • the term “average” refers to number average unless indicated otherwise.
  • % by weight As used herein, the terms “% by weight”, “wt.- %”, “weight percentage”, or “percentage by weight” are used interchangeably. The same applies to the terms “% by volume”, “vol.- %”, “vol. percentage”, or “percentage by volume”, or “% by mol”, “mol- %”, “mol percentage”, or “percentage by mol”.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1, 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g., from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • amorphous as used herein means a solid in which there is no long-range order of the positions of the atoms, in contrast to solids in which there is long-range atomic order which are called crystallized solids.
  • the “amorphous” or “crystalline property” of a catalyst support, i.e., also of the catalyst support of the invention, may be shown by X-ray diffraction spectroscopy (XRD).
  • anogel used herein means a solid and rigid material of a bonded, cross-linked macromolecule frame (network) obtained from corresponding monomers, for example a SiCh network, also called silica gel.
  • anhydrous as used herein means a substance which does not contain water.
  • aluminium gel for example is hydrous not anhydrous.
  • the anhydrous source may indeed be provided within a solution or a suspension but is nevertheless classed as anhydrous.
  • the present invention relates to an anthraquinone process (AO) for the manufacture of hydrogen peroxide, wherein the hydrogenation step is carried out with a catalyst in the form of catalyst powder particles having a mean particle size between 100 pm and 200 pm, used in a slurry, and wherein the catalyst comprises Pd, at least one other metal, and an amorphous catalyst support comprising silicon dioxide and alumina (SiAlOx) in an aerogel-physical form, wherein the alumina is incorporated into the silicon dioxide structure at the molecular level.
  • AO anthraquinone process
  • the catalyst consists of Pd, at least one other metal, and an amorphous catalyst support comprising silicon dioxide and alumina (SiAlOx) in an aerogel -physical form, wherein the alumina is incorporated into the silicon dioxide structure at the molecular level.
  • the catalyst is used in the form of catalyst powder particles in a slurry for the hydrogenation of a chosen quinone to the hydrogenated quinone.
  • the catalyst powder particles have a mean particle size of between 100 and 200 pm determined by methods well known by a person skilled in the art, for example by sieving or determination by laser granulometry.
  • the catalyst powder particles have a mean particle size between 110 and 190 pm, more preferably between 120 and 180 pm, even more preferably between 130 and 170 pm.
  • the catalyst used in the AO-process of the invention comprises in addition to Pd at least one other metal, preferably selected from the group consisting of Fe, Cu, Co, Ni, Sn, Ga, Zn, Au, Ag, Pt, Bi and Ru, or a combination thereof. More preferably, the at least one other metal is Co, Ni, Au, Ru or mixture thereof.
  • the catalyst comprises in addition to Pd one, two, up to five other types of metal as active component, which are selected from the group as defined above.
  • the catalyst comprises one, two or three other types of metal in addition to Pd.
  • the catalyst is a bimetallic catalyst, i.e., the catalyst comprises Pd and one other type of metal.
  • the Pd as well as the at least one other metal can be in the elemental state or in the form of a compound, such as a salt or an oxide.
  • the catalyst preferably comprises Pd and the at least one other metal in the elemental state.
  • the amount of Pd present in the catalyst is preferably of from 0.1 to 2.5 wt.- % based on the total amount of the catalyst. More preferably the amount is from 0.1 to 2.0, even more preferably from 0.2 to 1.5 wt.-%, most preferably 0.3 to 1.0 wt.-%, based on the total amount of the catalyst.
  • the at least one other metal is used in an amount in the catalyst of preferably from 0.01 wt.-% to 2.0 wt.-%, more preferably of from 0.05 to 1.5 wt.-% even more preferably of from 0.1 to 1.0 wt.-%, based on the total amount of the catalyst.
  • the amount of the metals presents in the catalyst used in the AO-process of the invention can be determined by any method known in the art, for example by using Inductively Couple Plasma Optical Emission Spectrometry (ICP-OES).
  • ICP-OES Inductively Couple Plasma Optical Emission Spectrometry
  • the catalyst used in the AO process of the invention is an amorphous supported catalyst.
  • the carrier of the catalyst comprises silicon dioxide and alumina (SiAlOx) in an aerogel -physical form, wherein the alumina is incorporated into the silicon dioxide structure at the molecular level, i.e., the silicon dioxide forms a bonded, cross-linked macromolecule frame (network), also called silica gel, wherein the alumina is incorporated at the molecular level.
  • the alumina is not only present on the exterior surface of the silica gel (for example as a coating) but also inside the silica gel.
  • This structure can be determined by using transmission electron microscopy (TEM) and/or scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometry (EDX). Due to this structure the resulting catalyst support is homogenous, by the opposition to a carrier, in which a first oxide would have been deposited and/or precipitated on a second oxide.
  • TEM transmission electron microscopy
  • SEM scanning electron microscopy
  • EDX energy dispersive X-ray spectrometry
  • Silica-based aerogels usually feature a mesoporous network, with interconnected pores of sizes typically ranging from 0.5 to 100 nm and average diameter between 5 and 40 nm. They have a low bulk density usually ranging from 0.03 to 0.8 g/cm 3 .
  • the amorphous catalyst support of the invention can be produced by any method known in the art, but, usually, the following two methods are used.
  • silicon dioxide is mixed with anhydrous source of alumina, for example sodium aluminate, at a pH level of above 11 and a temperature of 30 to 90 °C for forming a suspension. Afterwards, the suspension is optionally washed with water and the catalyst support is separated from water, dried and/or calcined.
  • alumina for example sodium aluminate
  • the such produced catalyst carrier comprises in addition to SiCE and alumina, also anions like Cl’, (CCE) 2 ’, (SCU) 2 ’; (NCE)’, in an amount not exceeding 10% by weight of the catalyst support, preferably, the amount of these anions is usually between 0.05 and 8 wt.-%, more preferably between 0.5 and 6 wt.-%, even more preferably between 1.0 and 3 wt.- %, based on the total weight of the support.
  • the amount of the anions present in the catalyst support may be measured by any method known in the art, as for example described in US 2012/01223138 Al.
  • alumina and silica sols are prepared separately in the presence of a liquid, usually ethanol, and HC1 and NH4OH as common acid and alkaline catalysts. Afterwards, the two sols are brought together in the presence of an appropriate catalyst to obtain an alumina-silica gel.
  • a silylation and drying step is carried out to obtain the desired amorphous catalyst support comprising silicon dioxide and alumina (SiAlOx) in an aerogel -physical form, wherein the alumina is incorporated into the silicon dioxide structure at the molecular level.
  • the amorphous catalyst support according to the invention preferably contains alumina in an amount of from 1 to 50 wt.-%, more preferably from 3 to 30 wt.-%, even more preferably from 5 to 10 wt.-%, based on the total weight of the amorphous catalyst support.
  • the catalyst support of the invention has preferably a spherical morphology.
  • the BET surface area of the amorphous catalyst support is preferably between 1 and 1000 m 2 /g, more preferably between 50 and 800 m 2 /g, even more preferably between 100 and 700 m 2 /g determined by a porosity measurement.
  • Pd and at least one other metal is deposited on the amorphous catalyst support as described above. This can be done by any suitable method known in the art.
  • the metals are deposited on the catalyst support by precipitation and/or impregnation, more preferably, both the at least one other metal and the Pd are deposited under precipitation conditions.
  • the source for Pd may be a palladium salt selected from chloride or acetate, preferably chloride, more preferably the source is EfcPdCU.
  • the source of the at least other metal is generally a salt selected from the group consisting of acetate, bromide, chloride, and nitrate.
  • the precipitation step is conducted preferably in basic medium having a pH in the range from 7 to 12, more preferably from 8 to 11.
  • the basic medium therefore can be obtained by using for example sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or ammonium carbonate.
  • the precipitation is carried out at a temperature of between 50 and 80 °C, more preferred between 55 and 75 °C, even more preferred between 60 and 70 °C.
  • the deposition of the Pd and the at least one other metal on the catalyst support can be carried out simultaneously or subsequently. According to the invention, it is preferred that in a first step the at least one other metal and subsequently Pd is deposited on the amorphous catalyst support.
  • the catalyst is filtered off, washed, preferably with demineralized water, optionally reduced to obtain the metals deposited on the catalyst support in elemental state, and dried.
  • the reduction step can be carried out by any method known in the art. Preferably by using a reducing agent selected from the group consisting of molecular hydrogen, hydrazine, hydrate, hydrogen containing gas, ascorbic acid, formic acid, and formaldehyde. The reduction is carried out preferably at a temperature between 20 and 200 °C, more preferably between 20 and 100 °C.
  • the deposited metals can have different locations on the amorphous catalyst support.
  • the metals may be concentrated in a thin layer close to the external surface of the support, this may be referred to as an “egg-shell mode or “egg shell profile”.
  • the metals may be concentrated in a thin layer below the surface, but not penetrating to the centre of the support, this may be referred to as an “egg-white mode (profile)”, the metals may be concentrated in a small zone near the centre of the support, this may be referred to as an “egg-yolk mode (profile)”, and the metals may be uniformly distributed throughout the support.
  • Pd and the at least one other metal show usually an egg-shell profile as determined by STEM & SEM-EDX analysis.
  • the Pd and at least one other metal are preferably located on the amorphous catalyst support in the form of particles. These metal particles have preferably a size between 1 and 50 nm, more preferably between 3 to 45 nm, as determined by STEM & SEM-EDX analysis.
  • the catalyst of the invention generally has an activity of at least 100% relative to the activity of the same catalyst in which the at least one other metal is replaced with Pd.
  • the catalyst shows a relative activity of at least 110% or at least 120 %, i.e., shows an improved activity relative to the activity of the same catalyst in which the at least one other metal is replaced with Pd.
  • the activity of the catalyst can be determined by measuring the rate of conversion of alkylanthraquinone into alkylanthrahydroquinone as for example described in US 2012/0123138 Al.
  • Example 1 Pd/Co/SiAlO x catalyst
  • the catalyst was prepared in two steps. Firstly, 10 g of the SiAlOx support was added to 30 ml of demineralized water and stirred at 250 rpm. 2 g of Na2COs was added and the reaction mixture was heated to 70 °C. 5.25 ml of an acidic C0Q2.6H20 solution (20 g Co/1) was added at a rate of 1 ml/min. The reaction mixture was stirred for 15 min. Afterwards, the mixture was decanted and washed 3 times with 30 ml of demineralized water. 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the concentration of metals deposited on the carrier SiAlOx was determined via ICP-OES.
  • the Pd concentration was 1 wt.-% and the Co concentration was 0.35 wt.-%.
  • the determined activity of said catalyst was 107 % of the relative activity of a 1.0 wt.%-Pd catalyst.
  • STEM & SEM-EDX analysis showed an egg-shell profile for both metals.
  • the metal particles, Pd & Co had a size between 3 and 17 nm, and the catalyst powder particles have a mean particle size of 120 pm determined by laser granulometry.
  • the catalyst was prepared in two steps. Firstly, 10 g of the SiAlOx support was added to 30 ml of demineralized water and stirred at 250 rpm. 2 g of Na2COs was added and the reaction mixture was heated to 70 °C. 3.5 ml of an acidic NiNCh solution (20 g Ni/1, NiNCh dissolved in diluted HC1)) was added at a rate of 1 ml/min. The reaction mixture was stirred for 15 min. Afterwards, the mixture was decanted and washed 3 times with 30 ml of demineralized water. 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water.
  • the catalyst was put in an oven at 110 °C to dry for 12 h.
  • the catalyst was again added to 30 ml of demineralized water, heated to 70°C and stirred at 250 rpm.
  • 5.25 ml FEPdCU solution (20 g Pd/1) was added at 1.7 ml/min. The mixture was stirred for 15 min. Afterwards, it was decanted and washed 3 times with 30 ml demineralized water.
  • 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water. The catalyst was put in an oven at 110°C to dry for 12h.
  • the concentration of metals deposited on the carrier SiA10 x was determined via ICP-OES.
  • the Pd concentration was 1 wt.-% and the Ni concentration was 0.10 wt.-%.
  • the determined activity of said catalyst was 121 % of the relative activity of a 1.0 wt.%-Pd catalyst.
  • STEM & SEM-EDX analysis showed an egg-shell profile for both metals.
  • the metal particles, Pd & Co had a size between 5 and 41 nm, and the catalyst powder particles have a mean particle size of 120 pm determined by laser granulometry.
  • the catalyst was prepared in two steps. Firstly, 10 g of the SiA10 x support was added to 30 ml of demineralized water and stirred at 250 rpm. 2 g of Na2CC>3 was added and the reaction mixture was heated to 70 °C. 1.05ml of an acidic AuCh solution (20 g Au/1)) was added at a rate of 1 ml/min. The reaction mixture was stirred for 15min. Afterwards, the mixture was decanted and washed 3 times with 30 ml of demineralized water. 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water.
  • the catalyst was put in an oven at 110 °C to dry for 12 h.
  • the catalyst was again added to 30 ml of demineralized water, heated to 70°C and stirred at 250 rpm.
  • 63 ml EfcPdCU solution (20 g Pd/1) was added at 1.7 ml/min. The mixture was stirred for 15 min. Afterwards, it was decanted and washed 3 times with 30 ml demineralized water.
  • 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water. The catalyst was put in an oven at 110 °C to dry for 12 h.
  • the concentration of metals deposited on the carrier SiA10 x was determined via ICP-OES.
  • the Pd concentration was 1.2 wt.-% and the Au concentration was 0.068 wt.-%.
  • the determined activity of said catalyst was 155 % of the relative activity of a 1.4 wt.%-Pd catalyst.
  • STEM & SEM-EDX analysis showed an egg-shell profile for both metals.
  • the metal particles, Pd & Co had a size between 4 and 22 nm, and the catalyst powder particles have a mean particle size of 120 pm determined by laser granulometry.
  • the catalyst was prepared in two steps. Firstly, 10g of the SiA10 x support was added to 30 ml of demineralized water and stirred at 250 rpm. 2 g of Na2CC>3 was added and the reaction mixture is heated to 70 °C. 1.05 ml of an acidic RuCh solution (20 g Ru/1) was added at a rate of 1 ml/min. The reaction mixture was stirred for 15min. Afterwards, the mixture was decanted and washed 3 times with 30ml of demineralized water. 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water.
  • the catalyst was put in an oven at 110 °C to dry for 12 h.
  • the catalyst was again added to 30 ml of demineralized water, heated to 70°C and stirred at 250 rpm.
  • 5.25 ml EfcPdCU solution (20 g Pd/1) was added at 1.7 ml/min. The mixture was stirred for 15 min. Afterwards, it was decanted and washed 3 times with 30ml demineralized water.
  • 30 ml of demineralized water was again added, and the mixture was heated to 50 °C at 250 rpm. 0.3 g formic acid (100%) was added.
  • the catalyst was again decanted and washed 3 times with 30 ml demineralized water.
  • the catalyst was put in an oven at 110 °C to dry for 12 h.
  • the concentration of metals deposited on the carrier SiA10 x was determined via ICP-OES.
  • the Pd concentration was 1 wt.-% and the Ru concentration was 0.08 wt.-%.
  • the determined activity of said catalyst was 130 % of the relative activity of a 1.2 wt.%-Pd catalyst.
  • STEM & SEM-EDX analysis showed an egg-shell profile for both metals.
  • the metal particles, Pd & Co had a size between 5 and 41 nm, and the catalyst powder particles have a mean particle size of 120 pm determined by laser granulometry.
  • the examples demonstrate that the activity of the supported bimetallic catalyst of the invention is in the same range or even better in comparison to the corresponding monometallic Pd-catalyst.

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Abstract

La présente invention concerne un procédé anthraquinone (AO) pour la fabrication de peroxyde d'hydrogène, l'étape d'hydrogénation étant conduite à l'aide d'un catalyseur comprenant en plus du palladium (Pd) au moins un autre métal, et un support de catalyseur amorphe.
PCT/EP2024/067243 2023-06-26 2024-06-20 Catalyseur d'hydrogénation pour la fabrication de peroxyde d'hydrogène Ceased WO2025002974A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202480043190.7A CN121463995A (zh) 2023-06-26 2024-06-20 用于制造过氧化氢的氢化催化剂
EP24735610.8A EP4731334A1 (fr) 2023-06-26 2024-06-20 Catalyseur d'hydrogénation pour la fabrication de peroxyde d'hydrogène

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23181566 2023-06-26
EP23181566.3 2023-06-26

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US2158525A (en) 1935-10-10 1939-05-16 Ig Farbenindustrie Ag Production of hydrogen peroxide
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US20120123138A1 (en) 2007-08-30 2012-05-17 Solvay (Societe Anonyme) Catalyst support and process for the preparation thereof
CN103301851A (zh) * 2013-06-07 2013-09-18 苏州市泰力达科技有限公司 一种蒽醌氢化催化剂的制备方法
CN111686721A (zh) * 2019-03-12 2020-09-22 山西潞安矿业(集团)有限责任公司 钯钌合金催化剂及其制备方法、应用
US20210023536A1 (en) * 2018-10-23 2021-01-28 Beijing University of Chemical Techhnology Supported bimetallic core-shell structure catalyst and its preparation method
CN112973726A (zh) * 2019-12-13 2021-06-18 山西潞安矿业(集团)有限责任公司 一种钯钴合金催化剂及其制备方法、应用

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CA600788A (en) * 1960-06-28 Gross Albert Process for the production of metallic hydrogenation catalysts
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US2215883A (en) 1937-04-07 1940-09-24 Walter H Duisberg Production of hydrogen peroxide
US20120123138A1 (en) 2007-08-30 2012-05-17 Solvay (Societe Anonyme) Catalyst support and process for the preparation thereof
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