EP3585515A1 - Système de catalyseurs à base d'argent à dépressurisation réduite pour la déshydrogénation oxydative des alcools - Google Patents

Système de catalyseurs à base d'argent à dépressurisation réduite pour la déshydrogénation oxydative des alcools

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Publication number
EP3585515A1
EP3585515A1 EP18705141.2A EP18705141A EP3585515A1 EP 3585515 A1 EP3585515 A1 EP 3585515A1 EP 18705141 A EP18705141 A EP 18705141A EP 3585515 A1 EP3585515 A1 EP 3585515A1
Authority
EP
European Patent Office
Prior art keywords
silver
catalyst
catalyst layer
range
layer
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.)
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Application number
EP18705141.2A
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German (de)
English (en)
Inventor
Ekaterina Troussard
Roman Daniel PILZ
Emil Roeth
Marco Bosch
Susanne Weber
Peter Loecher
Daniel Pfeiffer
Thomas Holtmann
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3585515A1 publication Critical patent/EP3585515A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver

Definitions

  • the present invention relates to an improved silver-containing catalyst system for the production of aldehydes and / or ketones by oxidative dehydrogenation of alcohols, in particular the oxidative dehydrogenation of methanol to formaldehyde, comprising a first catalyst layer and a second catalyst layer, wherein the first catalyst layer consists of a silver-containing material in the form of coils, nets or knitted fabrics having a basis weight of 0.3 to 10 kg / m 2 and a wire diameter of 30 to 200 ⁇ , and the second catalyst layer of a silver-containing material in the form of granules having an average particle size of 0, 5 to 5 mm, and the two catalyst layers are in direct contact with each other.
  • the invention further relates to a corresponding process for the preparation of aldehydes and / or ketones, in particular of formaldehyde, by oxidative dehydration of corresponding alcohols on a silver-containing catalyst system.
  • oxidative dehydrogenation is the conversion of alcohols to corresponding aldehydes and / or ketones in the presence of an oxygen-containing gas mixture, preferably oxygen, wherein at least a portion of the hydrogen formed is converted into water with oxygen.
  • the reaction can take place in both the gas phase and the liquid phase, with preference being given to conducting in the gas phase.
  • electrolytically produced silver crystals are used as catalyst.
  • silver in an electrolytic cell is anodically oxidized to silver ions and cathodically reduced back to silver.
  • the coarsely crystalline silver formed at the cathode is suitable as a catalyst for the synthesis of formaldehyde from methanol. Particularly good results can be achieved with the fixed bed catalysts described in DE 2322757 A.
  • Suitable silver crystals are obtained in particular by means of the electrolysis described in DE 1 166171 B.
  • the electrolyte used is preferably an aqueous silver nitrate solution.
  • This silver nitrate solution generally has a pH of 1 to 4 and contains 1 to 5 wt .-% silver.
  • the pH is preferably adjusted with nitric acid.
  • the electrodes used are the electrodes customarily used in the electrolysis of silver.
  • Suitable anodes are sacks in which the silver to be oxidized has generally been introduced as granules or as a powder.
  • Particularly suitable as cathodes are silver sheets.
  • the electrolysis is preferably carried out at current densities of 80 to 500 A per m 2 of cathode surface and electrolyte temperatures of 10 to 30 ° C. guided. To reach these current densities, voltages of 1 to 15 volts are required for most electrolysis cells. It is advisable to continuously remove the silver crystals formed at the cathode from the cathode. Silver crystals having a grain size of 0.2 to 5 mm are generally obtained.
  • the silver crystals are assigned to starting silver catalyst fixed beds consisting of 1 to 9 layers of silver crystals (so-called “short layers”) with a total layer thickness of 1 to 10 cm.
  • the sponge-like structure does not stop during the manufacturing process, but leads to ever finer distributed silver filaments and ever narrower free spaces in the sponge structure.
  • the conversion of at least a portion of the silver crystals of these catalysts, which typically consist of electrolytic silver crystals in the size range of 0.2 mm to 5 mm, to the spongy structure explains the observation that in a freshly incorporated silver crystal catalyst, the conversion and selectivity in the Operation initially increase.
  • the ever-finer sponge structure leads to an increase in the pressure loss on the catalyst, which increases the proportion of non-selective gas-phase reactions and decreases the selectivity for the product (for example formaldehyde).
  • the typical service life is 0.5 to 4 months.
  • DE 2829035 A describes a catalyst of catalytically active metal fibers, which consist of silver, platinum, rhodium, palladium or an alloy based on one of these metals, wherein the metal fibers are felt-like interconnected in the manner of a needle composite material.
  • the catalyst can be used for ammonia oxidation, hydrocyanic acid or formaldehyde production.
  • the cross-section of a ribbon-shaped fiber may be rectangular with the dimensions 50 and 100 ⁇ , and the length between 10 cm and 1 m.
  • the catalyst body is produced by melt spinning or melt extraction. For example, it is made from a tape of 1 to 2 mm width and 50 to 60 ⁇ thickness Shrinking (imprinting of a wave profile) and cutting about 1 cm long, thus rather openfaserige, wavy catalyst body obtained.
  • WO 2012/146528 describes a process for the preparation of C 1 -C 10-aldehydes by oxidative dehydrogenation of C 1 -C 10 alcohols on a shaped catalyst body which can be obtained by three-dimensional shaping and / or arranging in the space of silver-containing fibers and / or filaments , characterized in that the average diameter or the average diagonal length of a substantially rectangular or square cross-section of these silver-containing fibers and / or filaments in the range of 30 to 200 ⁇ .
  • the teaching of combining the two materials to elicit the beneficial effects of the present invention is lacking.
  • WO 2015/086703 describes a process for producing metal foam bodies wherein the metal M (x) is present either as a pure substance or as a mixture with metal M (y) and the metals M (x) and M (y) from a group consisting of nickel , Chromium, cobalt, copper and silver, as well as the use of such metal foam bodies as a catalyst for the production of formaldehyde from methanol.
  • a combination of silver-containing metal foams with other silver-containing catalyst moldings for the production of formaldehyde from methanol is not mentioned in this document.
  • No. 3,959,383 describes a two-stage process using in the first stage a silver catalyst consisting of fibrous electrolytic silver, crystalline electrolytic silver or silver on a support such as alumina, and in the second stage a crystalline electrolytic silver catalyst.
  • the two-stage process is further characterized by the fact that the first and the second stage respectively in spatially separated reactors under adiabatic conditions at 575 ° C to 650 ° C and 600 ° C to 700 ° C, and that the temperature of the reaction gas after the first stage by means of a heat exchanger is actively cooled to ⁇ 300 ° C before it is driven with additional oxygen dosage in the second stage.
  • CN 100435943 C describes a catalyst system for the conversion of methanol to formaldehyde from two layers arranged in parallel, the first layer consisting of fibrous electrolytic silver and the second layer of crystalline electrolytic silver.
  • the proportions are 10 to 35 wt .-% for the first layer and 65 to 90% by weight for the second layer.
  • the particle size of the crystal-like electrolytic silver is in the The range of 8 to 24 mesh (corresponding to 2.38 to 0.74 mm) and that of the fibrous electrolytic silver is in the range of 32 to 40 mesh (corresponding to 0.55 to 0.40 mm).
  • the object of the present invention is to provide an improved silver-containing catalyst system for the preparation of C 1 -C 10-aldehydes and / or ketones by oxidative dehydrogenation of the corresponding C 1 -C 10 alcohols, in particular the oxidative dehydrogenation of methanol to formaldehyde, or to provide appropriate manufacturing method in which under reaction conditions, the pressure loss and in particular the increase in the pressure loss, which is caused by the catalyst system, low and the selectivity is high, and at the same time a high conversion is achieved.
  • These improved properties of the catalyst system prolongs the run time of the system, suppresses the proportion of nonselective side reactions in the gas phase and reduces the cost of compression of the fresh gas mixture.
  • the pressure loss and the pressure loss increase under reaction conditions over the entire catalyst system should be at a lower level, with at least the same activity and / or selectivity.
  • the object is achieved by providing the silver-containing catalyst system according to the invention or the process according to the invention for preparing aldehydes and / or ketones by oxidative dehydrogenation of corresponding alcohols on such a silver-containing catalyst system.
  • the silver-containing catalyst system according to the invention comprises
  • a first catalyst layer A of a silver-containing material which is in a form of wires selected from the group consisting of coils, nets and knits, and
  • a second catalyst layer B of a silver-containing material which is in the form of granules having an average particle size in the range of 0.5 to 5 mm,
  • the catalyst layer B is in direct contact with the catalyst layer A, characterized in that the silver-containing material of the catalyst layer A
  • the silver-containing material of the catalyst layer A is in a form selected from the group consisting of balls, nets and knits, preferably in the form of nets or crocheted.
  • the silver-containing material of the catalyst layer A is preferably electrolytic silver, preferably in a purity (silver content in% by weight) of> 98%, preferably> 99%, more preferably> 99.9% and in particular> 99.99%.
  • the silver-containing material of the catalyst layer B is preferably electrolytic silver, preferably in a purity (silver content in wt .-%) of> 30%, preferably> 50%, more preferably> 90%, most preferably> 99.9% and in particular ä 99.99%.
  • the silver-containing material of the catalyst layer A and / or the catalyst layer B is phosphorus-doped.
  • Silver-containing fibers or filaments are known to the person skilled in the art, are commercially available and are used, for example, as electrical conductor material, in high-grade textiles or in corrosion-resistant, sensory applications (for example pH determination).
  • the three-dimensional deformation and / or arranging the silver-containing fibers or threads in space can be done disorderly or ordered.
  • the disordered deformation and / or arranging the silver-containing fibers according to the invention or preferably silver-containing threads according to the invention leads to the inventive balls. They can be produced, for example, by the fibers or threads (possibly also arrangements of fibers or threads, such as nets or knits) packed into a statistically irregularly arranged ball and then under pressure to the desired ball density or the desired void content in the Hanks continue to be compressed.
  • the silver-containing fibers or filaments according to the invention are arranged irregularly in space and can also be entangled with one another in a felt-like manner, thereby obtaining, for example, their particular mechanical stability.
  • the pore diameter is determined by an optical comparison of the cell diameter of a selected cell of the metal foam body using calibrated ring sizes, imaged on a sheet of transparent paper placed on the metal foam body.This measurement is carried out for at least a hundred different cells, the mean of these measurements giving the pore diameter.
  • the apparent density is determined according to DIN EN-ISO 845 (Oct. 2009, "Foams made of rubber and plastics - Determination of bulk density").
  • the specific geometric surface area (GSA) and porosity is determined according to the method described in WO
  • KR 100921399 B describes a process for the preparation of open-celled silver foams containing no impurity on platinum by pre-treating a polyurethane foam with a sodium hydroxide solution followed by an electrolytic application of silver and a heat treatment of the silver-containing polyurethane foam at temperatures in the range from 800 to 950 ° C.
  • the silver-containing foam according to the invention is preferably produced according to WO 2015/086703.
  • the silver-containing foam can also be treated according to DE 4424157 A in order to optimize the anisotropic properties, in particular with respect to the thermal and electrical conductivity, for use as a catalyst for the production of formaldehyde from methanol.
  • the granules according to the invention are granular material consisting of small, usually irregularly shaped, solid particles, preferably electrolytically produced silver crystals.
  • the wire diameter corresponds to the average diameter or the average diagonal length of the wires (fibers or filaments) of knots, nets or knitted fabrics of knots, nets or knitted fabrics.
  • the average diameter (for a substantially circular cross-section) of the silver-containing fibers or filaments is determined according to DIN ISO 4782 (Oct. 1993, "Metal wire for industrial screen mesh") by means of external micrometer.
  • the average diagonal length (for a substantially rectangular or square cross-section) of the silver-containing fibers or filaments is also determined in an analogous manner by means of an external micrometer (measurement of height and width and calculation of the diagonal length).
  • the mean particle size of the granules can be determined according to the method according to DIN 66165-1 and 66165-2 (August 2016) ("Particle size analysis - sieve analysis").
  • the wire diameter of the silver-containing material of the catalyst layer A is in the range of 30 ⁇ to 200 ⁇ , preferably in the range of 30 ⁇ to 150 ⁇ and in particular in the range of 30 ⁇ to 70 ⁇ .
  • the threads or fibers of this knot, nets or knits have a substantially circular cross-section, particularly preferably the threads or fibers of this knot, nets or knitted fabrics have a circular cross-section.
  • the average particle size of the silver-containing material of the catalyst layer B is in the range of 0.5 mm to 5 mm, preferably in the range of 0.75 mm to 4 mm and in particular in the range of 1 mm to 3 mm.
  • the layer height of the catalyst layer B is at least 10 mm, preferably at least 15 mm, particularly preferably at least 20 mm and in particular at least 25 mm in order to obtain the most uniform possible height distribution of the catalyst layer B over the cross section of the catalyst bed diameter .
  • the layer height of the catalyst layer B varies over the catalyst bed diameter over the catalyst bed diameter with the aim of achieving a height specification optimally uniform flow through the entire catalyst bed, so that the catalyst bed is optimally utilized.
  • the catalyst layers A and B can each consist of different sublayers, which are characterized by different silver-containing materials or different forms of the silver-containing materials (for example sublayers of catalyst layers B with granules of different particle size, or, for example in the case of nets, sublayers of Catalyst layers A with meshes of different mesh size).
  • the catalyst layers A and B are each not constructed in sub-layers.
  • the average particle size for the catalyst layer B is too low, or if an unsuitable shape is used, then the fine-structured silver layer forming from the silver-containing material of the catalyst layer A will over-fill the free spaces between the silver-containing material in the catalyst layer B and result in a increased pressure loss or pressure loss increase. If the average particle size for the catalyst layer B is too large or an improper shape is used, the formation of the fine-structured silver layer is insufficient and the catalyst activity is too low.
  • reaction conditions are understood as meaning the passage of reactant stream comprising one or more C 1 -C 10 alcohols and one or more oxidative agents through the catalyst system at a temperature in the range from 350 to 750 ° C., a space velocity between 36,000 r 1 and 1 .800.000 h "1 and a face velocity of between 0.1 ms and 15 ms _1 _1.
  • the one or more oxidative agents in a proportion of 0.01 wt .-% 9 is inserted based on the total feed stream.
  • the educt stream contains inert gases such as nitrogen and / or additives such as halogenated hydrocarbons, for example C 2 H 4 Cl 2 or C 2 H 2 Cl 2, the additives preferably being used in the ppm range (for example a maximum of 500 ppm by weight) based on the educt stream.
  • inert gases such as nitrogen
  • additives such as halogenated hydrocarbons, for example C 2 H 4 Cl 2 or C 2 H 2 Cl 2
  • the additives preferably being used in the ppm range (for example a maximum of 500 ppm by weight) based on the educt stream.
  • the catalyst system according to the invention is the activated catalyst system in which the silver-containing material of the catalyst layer A has been wholly or partially converted to a finely structured silver layer on the silver-containing material of the catalyst layer B, or to the original catalyst system, before such a reaction of the catalyst layer A.
  • the educt stream flows through a catalyst system (reaction zone) according to the invention.
  • the educt stream flows through a plurality of catalyst systems according to the invention (reaction zones) which are connected in "series.” This series connection can be realized in a reactor or in a reactor cascade.
  • Such carrier devices are known, for example, grids, baskets or perforated plates or sturdy nets of various materials, preferably of metals, for example stainless steel or silver.
  • the educt stream is preferably gaseous.
  • Suitable C 1 -C 10 alcohols for the process according to the invention or for the reaction conditions according to the invention are alcohols having 1 to 10 carbon atoms and one or more, preferably one to three, OH groups.
  • the alcohols preferably have one or two OH groups, very particularly preferably an OH group.
  • the alcohols have at least one secondary or primary OH group, preferably at least one primary OH group.
  • the alcohols may be aliphatic, linear, branched or cyclic, containing one or more C-C double or triple bonds in the molecule. They may be aliphatic alcohols or aralkyl alcohols, preferably aliphatic alcohols. Preference is given to primary alcohols or, in the case of dihydric alcohols, to vicinal C 1 -dodiols.
  • the C 1 -C 10 -alcohols are preferably selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 1,2-ethanediol (ethyleneglycol), 1, 2-propanediol, 1, 3-propanediol, 2- (2-hydroxyethoxy) ethanol (diethylene glycol), allyl alcohol, 3-methyl-2-butenol (prenol) and 3-methyl-3-butenol (iso-prenol).
  • Particularly preferred Ci-Cio-alcohol is methanol.
  • C 1 -C 10-aldehydes are formaldehyde (methanal), glyoxal (ethanedi al), 2-hydroxyethanal (glycolaldehyde), 2- (2-hydroxyethoxy) ethanal, 3-methyl-2-butenal (prenal) and Methyl-3-butenal (iso-prenal).
  • both pure oxygen and preferably oxygen-containing gas mixtures such as air, as well as other oxidative gases such as nitrogen oxide (NO), nitrogen dioxide (N0 2 ), nitrous oxide (N 2 O), nitrous oxide (N 2 O 4), or mixtures thereof.
  • methanol is converted to formaldehyde (methanal).
  • Suitable starting materials for this purpose are pure methanol, technical methanol, produced by a high or low pressure process crude methanol or, advantageously, their mixtures with water.
  • the mass fraction of the methanol in such aqueous mixtures is advantageously 30 to 99 wt .-%, preferably 45 to 97 wt .-%, particularly preferably 60 to 95 wt .-%, preferably 70 to 90 wt .-%.
  • crude methanol is used which has been purified by the methods described in DE 1277834 B, DE 1235881 C or DE 136318 C by separating a lower-boiling fraction or by treatment with oxidants and / or alkalis.
  • oxygen and methanol are expediently in a molar ratio of 0.1: 1 to 1, 0: 1, preferably 0.25: 1 to 0.6: 1, particularly preferably 0.35: 1 to 0.5: 1 used.
  • the methanol is preferably supplied to the reactor space in vapor form, advantageously in admixture with steam and optionally with an inert gas.
  • an inert gas for example, nitrogen may be considered as the inert gas
  • the proportion of inert gas relative to the gaseous methanol and water mixture may be varied and is usually between 0.1 and 30 vol.%, Preferably between 0.15 and 20 vol. %, more preferably between 0.2 and 10 vol.%, preferably between 0.3 and 5 vol.%.
  • the above-described reaction mixture is generally at a temperature in the range from 50 to 200 ° C and usually at an absolute pressure in the range of 0.5 bar to 2 bar, preferably from 1, 0 to 1, 7 bar introduced into the reactor.
  • the reaction gases leaving the reaction zone are cooled within a few seconds, for example within a maximum of 10 seconds, e.g. to temperatures in the range of 50 to 350 ° C.
  • the cooled gas mixture is then expediently fed to an absorption tower in which the formaldehyde is washed with water or an aqueous formaldehyde / urea solution, preferably in countercurrent, from the gas mixture.
  • Special variants of the generally known process for the preparation of formaldehyde which can also be used in the process according to the invention, are described in DE 2444586 A, DE 2451990 A, EP 83427 A and EP 150436 A.
  • the inventive catalyst system or the inventive method allows compared to conventional catalyst systems or processes a lower pressure drop and / or increase in pressure loss with the same or better yield and selectivity of the oxidative dehydrogenation of Ci-Cio alcohols to the corresponding aldehydes or ketones, in particular the oxidative Dehydrogenation of methanol to formaldehyde.
  • the catalyst system according to the invention or the process according to the invention enables longer catalyst service lives.
  • the catalyst system according to the invention or the process according to the invention enables comparable or better yield and selectivity of the oxidative dehydrogenation with lower catalyst mass.
  • FIG. 1 Schematic representation of the arrangement of the catalyst system according to the invention for the oxidative dehydrogenation of methanol to formaldehyde with a catalyst bed consisting of a first catalyst layer A (possibly in the form of several sub-layers) and a second catalyst layer B (possibly in the form of several sub-layers) on a C edition.
  • the starting material stream (the fresh gas) X containing methanol, oxygen, water and optionally nitrogen and formaldehyde, flows through the catalyst bed and the reaction gas Y containing methanol, water, hydrogen, carbon monoxide, carbon dioxide, formaldehyde and optionally Nitrogen and oxygen.
  • Figure 2 Schematic representation of the experimental setup used for the examples.
  • the reactants air (1), nitrogen (2), deionized water (3) and methanol (4) are in a reactor column (5) with preheating section (5a), catalyst packing (5b), electric heater (6) and quench cooler (7 ).
  • the resulting product mixture is passed into an absorption column (8) and transferred from the bottom of the absorption column (9) in a condenser (10).
  • the product is purified in a phase separator (1 1) with a cryostat (12).
  • the experiments were carried out in an adiabatic manner in a quartz glass reactor with an inner diameter of 20 mm and filled with catalyst.
  • the Adiabasie of the reactor was achieved by passive isolation and completely dispenses with a compensation heating.
  • the reactions were carried out with a gaseous water / methanol mixture (molar ratio of water / methanol: 1, 0), air (410 Nl / h) and nitrogen (150 Nl / h) to the extent that the molar ratio of methanol to Oxygen was 2.5.
  • This mixture was heated to 140 ° C. in a preheater upstream of the reactor and passed through the reactor.
  • the catalyst bed When the metering and preheater temperature is set as described above, the catalyst bed usually reaches temperatures in the range of 590 ° C to 710 ° C with ignited adiabatic reaction.
  • the space velocity typically ranges from 85,000 h -1 to 120,000 r 1 .
  • the product mixture leaving the catalyst bed is cooled directly to 120 ° C. on a heat exchanger.
  • the composition of the product mixture is determined by gas chromatographic analysis.
  • the methanol conversion is defined as the molar amount of methanol reacted divided by the molar amount of methanol used.
  • the formaldehyde selectivity is defined as the molar amount of formaldehyde formed divided by the molar amount of methanol reacted.
  • the use number as a measure of the selectivity of the reaction of methanol to formaldehyde given conversion, is defined as the amount of methanol in kilograms that must be supplied to the reactor system, so that in the reactor 1, 00 kilograms of formaldehyde is generated.
  • the initial activation of the catalyst on the one hand and the increasing pressure loss on the other hand in the later time lead to the number of operations through the operating time an optimum (minimum).
  • the average feed number, the average methanol conversion and the mean formaldehyde selectivity are determined cumulatively over a period of 18.5 days from the attainment of the respective feed number optimum.
  • the temperature measurement is carried out by means of temperature sensors, which are installed distributed over the cross section in the catalyst bed.
  • Comparative Example 1 two-layer catalyst with granules of electrolytic silver
  • the reactor was filled with a two-layer catalyst bed.
  • the lower layer consists of a granulate of electrolytic silver with a particle size between 1 and 2 mm and is on average 25 mm thick.
  • the purity of the silver is 99.99% and the basis weight of this layer is 34 kg / m 2 .
  • the upper layer consists of a granulate of electrolytic silver with a particle size between 0.5 and 1 mm and is on average 5 mm thick.
  • the purity of the silver is 99.99% and the basis weight of this layer is 10.8 kg / m 2 .
  • the catalyst is loaded at a space velocity of 100,000 r 1 .
  • the average flow velocity is 1, 12m / s.
  • the initial pressure drop across the reactor is 65 mbar.
  • the rate of increase in pressure loss is 0.81 mbar per day.
  • the average use number is 1, 214, the average methanol conversion is 96.6% and the mean formaldehyde selectivity is 90.9%, each cumulatively determined for a period of 18.5 days, starting with the time of the iere optimum, 0.5 Days after the start of formaldehyde production.
  • Comparative Example 2 single layer catalyst with silver wire mesh
  • the reactor was filled with layers of silver wire mesh.
  • the wire knit consists of silver wires with a wire diameter of 50 ⁇ m.
  • the purity of the silver is 99.99% and the basis weight of this layer is 18.4 kg / m 2 .
  • the layers of silver wire knit are 5 mm thick.
  • the catalyst is loaded at a space velocity of 800,000 h -1 .
  • the average flow velocity is 1, 12 m / s.
  • the initial pressure drop across the reactor is 88 mbar.
  • the rate of increase in pressure loss is 12.23 mbar per day.
  • Example 1 two-layered catalyst with silver wire mesh and granules of electrolytic silver
  • the reactor was filled with a two-layer catalyst bed.
  • the lower layer consists of granules of electrolytic silver with a particle size between 1 and 2 mm and is on average 20 mm thick.
  • the purity of the silver is 99.99% and the basis weight of this layer is 22.7 kg / m 2 .
  • the upper layer consists of individual layers of a Silberdrahtgestricks with a wire diameter of 50 ⁇ and is 0.5 mm thick in total.
  • the purity of the silver is 99.99% and the basis weight of this layer is 1.8 kg / m 2 .
  • the catalyst is loaded at a space velocity of 220,000 r.sup.- 1 .
  • the average flow velocity is 1.29 m / s.
  • the initial pressure drop across the reactor is 60 mbar.
  • the rate of increase in pressure loss is 0.27 mbar per day.
  • the average use number is 1, 21 1
  • the average methanol conversion is 97.3%
  • the average formaldehyde selectivity is 90.5%, each cumulative for a period of 18.5 days, starting with the time of the insert count optimum, 4.9 days after the start of formaldehyde production.
  • Example 2 two-layer catalyst with silver wire mesh and granules of electrolytic silver
  • the reactor was filled with a two-layer catalyst bed.
  • the lower layer consists of granules of electrolytic silver with a particle size between 1 and 2 mm and is on average 20 mm thick.
  • the purity of the silver is 99.99% and the basis weight of this layer is 22.7 kg / m 2 .
  • the upper layer consists of two superimposed woven nets of silver wire with a wire diameter of 100 ⁇ and is a total of 2 mm thick.
  • the mesh size of the net is 25 mesh, the purity of the silver is 99.99% and the basis weight of this layer is 3.3 kg / m2 .
  • the catalyst is loaded at a space velocity of 190,000 r.sup.- 1 .
  • the average flow velocity is 1.12 m / s.
  • the initial pressure drop across the reactor is 48 mbar.
  • the rate of increase in pressure loss is 0.55 mbar per day.
  • the average use number is 1, 213, the average methanol conversion is 97.2% and the mean formaldehyde selectivity is 90.5%, each cumulatively determined for a period of 18.5 days, starting with the time of the insert count optimum, 27.5% Days after the start of formaldehyde production.

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

L'invention concerne un système catalytique contenant de l'argent destiné à la préparation d'aldéhydes et/ou de cétones par déshydrogénation oxydative d'alcools, en particulier la déshydrogénation oxydative du méthanol en formaldéhyde, le système comprenant une première couche de catalyseur et une deuxième couche de catalyseur. La première couche de catalyseur est constituée d'un matériau contenant de l'argent sous forme de serpentins, de filets ou de tricots avec un grammage de 0,3 à 10 kg/m2 et un diamètre de fil de 30 à 200 μm et la deuxième couche de catalyseur est constituée d'un matériau contenant de l'argent sous la forme de granulat ayant une taille de particule moyenne de 0,5 à 5 mm, et les deux couches de catalyseur sont en contact direct l'une avec l'autre. L'invention concerne en outre un procédé correspondant de préparation d'aldéhydes et/ou de cétones, en particulier de formaldéhyde, par déshydrogénation oxydative d'alcools correspondants sur un système de catalyseurs contenant de l'argent.
EP18705141.2A 2017-02-24 2018-02-14 Système de catalyseurs à base d'argent à dépressurisation réduite pour la déshydrogénation oxydative des alcools Withdrawn EP3585515A1 (fr)

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PCT/EP2018/053604 WO2018153736A1 (fr) 2017-02-24 2018-02-14 Système de catalyseurs à base d'argent à dépressurisation réduite pour la déshydrogénation oxydative des alcools

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US20220388936A1 (en) * 2019-11-15 2022-12-08 Celanese International Corporation Process for converting methanol to formaldehyde
CN111545047A (zh) * 2020-04-29 2020-08-18 江苏卓高环保科技有限公司 一种除甲醛除臭杀菌一体式材料及其在除臭净化器上的应用
EP4367091A1 (fr) * 2021-07-08 2024-05-15 Hexion Inc. Procédés de synthèse d'aldéhydes
WO2023099727A1 (fr) 2021-12-03 2023-06-08 Basf Se Procédé de préparation d'isoprénaux et/ou de prénal

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