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WO2025168783A1 - Catalyseur à base d'oxyde supporté comprenant du tantale avec un rendement élevé dans la production de 1,3-butadiène - Google Patents

Catalyseur à base d'oxyde supporté comprenant du tantale avec un rendement élevé dans la production de 1,3-butadiène

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Publication number
WO2025168783A1
WO2025168783A1 PCT/EP2025/053271 EP2025053271W WO2025168783A1 WO 2025168783 A1 WO2025168783 A1 WO 2025168783A1 EP 2025053271 W EP2025053271 W EP 2025053271W WO 2025168783 A1 WO2025168783 A1 WO 2025168783A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide catalyst
range
supported oxide
butadiene
supported
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.)
Pending
Application number
PCT/EP2025/053271
Other languages
English (en)
Inventor
Parag Rasiklal Shah
Yatao Rachel Hu
Ewelina JANKOWIAK
Magdalena Sitko
Joanna KRYCA
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.)
Synthos SA
Ecovyst Inc
Original Assignee
Synthos SA
Ecovyst Inc
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 Synthos SA, Ecovyst Inc filed Critical Synthos SA
Publication of WO2025168783A1 publication Critical patent/WO2025168783A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/0205—Impregnation in several steps
    • 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
    • B01J37/0213—Preparation of the impregnating solution
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid

Definitions

  • Supported oxide catalyst comprising tantalum with high yield in the production of 1 ,3- butadiene
  • the present invention relates to a supported oxide catalyst comprising tantalum and having a specific average pore diameter. Moreover, the invention relates to a catalyst reaction tube for the production of 1 ,3-butadiene comprising at least one packing of the supported oxide catalyst as defined herein, to a fixed-bed reactor for the production of 1 ,3-butadiene comprising one or more of the catalyst reaction tubes as defined herein, and to a plant for the production of 1 ,3-butadiene comprising one or more of the fixed-bed reactors as defined herein. The invention also relates to a process for the production of 1 ,3-butadiene as defined herein.
  • 1 ,3-Butadiene is one of the most important raw materials in the synthetic rubber industry, where it is used as a monomer in the production of a wide range of synthetic polymers, such as polybutadiene rubbers, acrylonitrile-butadiene-styrene polymers, styrenebutadiene rubbers, nitrile-butadiene rubbers, and styrene-butadiene latexes.
  • 1 ,3-Butadiene is, for example, obtained as a by-product of ethylene manufacturing in naphtha steam cracking and can be isolated by extractive distillation (Chem. Soc. Rev., 2014, 43, 7917; ChemSusChem, 2013, 6, 1595; Chem. Central J., 2014, 8, 53).
  • the conversion of ethanol, obtainable e.g. from biomass, to 1 ,3-butadiene may be performed in two ways reported in the literature: as one-step process (Lebedev process) and as two-step process (Ostromislensky process).
  • the so-called two-step process may be performed by converting, in a first step, ethanol to acetaldehyde.
  • the aim of this first step is to feed a second step or fixed-bed reactor with such mixture of ethanol and acetaldehyde.
  • conversion of the mixture of ethanol and acetaldehyde to 1 ,3-butadiene over, for example, a silica-supported tantalum catalyst takes place (Catal. Today, 2016, 259, 446).
  • WO2022165190A1 relates to a method for making a supported tantalum oxide catalyst precursor or catalyst with controlled Ta distribution and the resulting supported Ta catalyst.
  • the method comprises selecting a Ta precursor with appropriate reactivity with the surface hydroxyls of the solid oxide support material to give a desired Ta distribution in the catalyst precursor or catalyst.
  • the method comprises controlling the number of surface hydroxyls available on the support material to react with the Ta precursor by thermal methods, such as calcining, to achieve the desired Ta distribution.
  • US 2018/0208522 A1 relates to a catalyst for the conversion of a feed comprising ethanol and acetaldehyde to 1 ,3-butadiene.
  • the catalyst comprises at least the element tantalum, and at least one mesoporous oxide matrix that has undergone an acid wash comprising at least 90% by weight of silica before washing, the mass of the element tantalum being in the range 0.1 % to 30% of the mass of said mesoporous oxide matrix.
  • the teaching of US 2018/0208522 A1 relies on acid washing of the mesoporous oxide support for increasing the selectivity of the catalyst towards 1 ,3-butadiene and/or the productivity of the catalyst towards 1 ,3-butadiene.
  • the catalyst contains amounts of sodium in the range of 0 to 500 ppm. Concentrations of aluminium in the catalysts and yields of 1 ,3-butadiene are not disclosed in US 2018/0208522 A1. Kim et al. (Chemical Engineering Journal 278 (2015) 217 - 223) teach the butadiene production from ethanol and acetaldehyde over tantalum oxide-supported spherical silica catalysts in a circulating fluidised bed. A Q10-supported catalyst was found to have an average pore diameter of about 150 A. The document further teaches that larger pore size results in a weaker catalyst and lower attrition resistance.
  • the present invention relates to a supported oxide catalyst comprising tantalum in an amount in a range of from 0.1 to 10 wt.%, calculated as Ta2 ⁇ 5 and based on the total weight of the supported oxide catalyst, the supported oxide catalyst having an average pore diameter in a range of from 180 to 245 A.
  • Average pore diameter is calculated using the following equation and assuming cylindrical pores: where surface area (SA) and pore volume (PV) are measured by Nitrogen Porosimetry using an Autosorb-6 Testing Unit from Anton Paar GmbH.
  • SA surface area
  • PV pore volume
  • the supported oxide catalyst is crushed into powder and samples of a weight of about 0.2 g each are used for analysis. Samples are first degassed at 350 °C for at least 4 hours on the Autosorb-6 Degassing Unit.
  • the multipoint surface area is calculated using the BET theory taking data points in the P/Po range 0.05 to 0.30.
  • the pore volume measurement is recorded at P/Po of 0.984 on the desorption leg.
  • tantalum-containing supported oxide catalysts according to the invention which contain a defined average pore diameter, demonstrate superior yield in 1 ,3-butadiene, and allow longer time on stream.
  • the supported oxide catalyst comprises (i) aluminium in an amount in a range of from 5 to 350 ppm and (ii) sodium in an amount in a range of from 35 to 500 ppm, each based on the total weight of the supported oxide catalyst.
  • the supported oxide catalyst comprises ⁇ aluminium in an amount in a range of from 5 to 60 ppm and (ii) sodium in an amount in a range of from 35 to 70 ppm, each based on the total weight of the supported oxide catalyst; or (i) aluminium in an amount in a range of from 50 to 350 ppm and (ii) sodium in an amount in a range of from 300 to 500 ppm, each based on the total weight of the supported oxide catalyst.
  • the supported oxide catalyst according to the invention has an average pore diameter in a range of from 180 to 240 A, preferably in a range of from 190 to 230 A, more preferably in a range of from 195 to 220 A, most preferably in a range of from 200 to 210 A.
  • the supported oxide catalyst according to the invention comprises tantalum in an amount in a range of from 0.5 to 5 wt.%, calculated as Ta2C>5 and based on the total weight of the supported oxide catalyst, more preferably in a range of from 2 to 3 wt.%, calculated as Ta2C>5 and based on the total weight of the supported oxide catalyst.
  • Supported oxide catalysts are advantageous because they allow control of the concentration and dispersion of the active sites, simple preparation of the catalyst by impregnation of any form and shape of the support, and easy access of the reacting molecules to all active sites of the catalyst.
  • the supported oxide catalyst comprises one or more of ordered and non-ordered porous silica supports, other porous oxide supports and mixtures thereof, preferably from ZrC>2, TiC>2, MgO, ZnO, NiO, and CeC>2,
  • the supported oxide catalyst comprises one or more of ordered and nonordered porous silica supports.
  • the supported oxide catalyst comprises non-ordered porous silica.
  • the supported oxide catalyst according to the invention has a BET specific surface area in a range of from 130 to 550 m 2 /g, preferably in a range of from 180 to 280 m 2 /g.
  • the supported oxide catalyst comprises (iv) calcium in an amount in a range of from 1 to 100 ppm, based on the total weight of the supported oxide catalyst. In one preferred embodiment, the supported oxide catalyst comprises (v) iron in an amount in a range of from 1 to 50 ppm, each based on the total weight of the supported oxide catalyst.
  • the supported oxide catalyst comprises (vi) titanium in an amount in a range of from 1 to 150 ppm, based on the total weight of the supported oxide catalyst.
  • the present invention relates to a catalyst reaction tube for the production of 1 ,3-butadiene comprising at least one packing of the supported oxide catalyst according to the invention, and one or more packings of inert material.
  • the inert material is selected from the group consisting of silicon carbide, inert ceramic beds, ceramic beads, extrudates, rings with a diameter in a range of 2 to 7 mm, stainless steel mesh, foams, and mixtures thereof.
  • the packings of the inert material contact and separate the packings of the supported oxide catalyst according to the invention, i.e. the reaction zones, from one another (if more than one packing of the supported oxide catalyst is present in the catalyst reaction tube). They are preferably located at the reactant feed inlet and outlet of the reaction tube.
  • the catalyst reaction tube is loaded with one packing of the supported oxide catalyst according to the invention, preferably in the centre of the catalyst reaction tube.
  • the supported oxide catalyst according to the invention is in contact with a packing of inert material on either side, i.e. the packings of inert material are preferably located at the feed inlet and outlet of the catalyst reaction tube.
  • the catalyst reaction tube comprises one reaction zone.
  • the catalyst reaction tube is loaded alternatingly with packings of the supported oxide catalyst according to the invention and packings of inert material.
  • the packings of inert material are preferably located at the feed inlet and outlet of the catalyst reaction tube and contact the packings of the supported oxide catalyst according to the invention.
  • the catalyst reaction tube comprises more than one reaction zone.
  • the present invention relates to a fixed-bed reactor for the production of 1 ,3-butadiene comprising one or more of the catalyst reaction tubes according to the invention.
  • the present invention relates to a plant for the production of 1 ,3- butadiene comprising one or more of the fixed-bed reactors as defined herein, and means for regenerating the supported oxide catalyst in said one or more fixed-bed reactors.
  • the plant also comprises an acetaldehyde-producing prereactor with one or more reaction tubes comprising a supported or unsupported (bulk) catalyst comprising one or more of zinc, copper, silver, chromium, and nickel, preferably comprising one or more of zinc and copper.
  • a supported or unsupported (bulk) catalyst comprising one or more of zinc, copper, silver, chromium, and nickel, preferably comprising one or more of zinc and copper.
  • Tantalum oxide as contained in the supported oxide catalyst according to the first aspect of the invention, is by itself inactive in the oxidation of ethanol to acetaldehyde.
  • the feed stream has to contain ethanol and acetaldehyde.
  • This mixture of ethanol and acetaldehyde can, for instance, be produced in the plant from ethanol in an acetaldehyde- producing pre-reactor comprising a supported or unsupported (bulk) catalyst as defined above, and then be fed into a fixed-bed reactor for the production of 1 ,3-butadiene comprising one or more of the catalyst reaction tubes according to the invention.
  • ethanol and acetaldehyde can be obtained from commercial sources and fed directly into a fixed-bed reactor for the production of 1 ,3-butadiene comprising one or more of the catalyst reaction tubes according to the invention.
  • the present invention relates to a process for the production of 1 ,3- butadiene, the process comprising
  • the (1) contacting takes place at a temperature in a range of from 200 to 500 °C, preferably from 250 to 450 °C, more preferably from 300 to 400 °C.
  • the (1) contacting takes place at a weight hourly space velocity in a range of from 0.2 to 10 IT 1 , preferably from 0.3 to 5 IT 1 , more preferably from 0.5 to 3 IT 1 .
  • the (1) contacting takes place at a pressure in a range of from 0 to 10 barg, more preferably from 1 to 3 barg, most preferably from 1 to 2 barg.
  • the process according to the sixth aspect of the invention further comprises the following step:
  • the (1) contacting takes place in a continuous flow of the feed in a fixed-bed reactor as per the third aspect.
  • the feed comprises at least 50 wt.% of ethanol, preferably comprises 60 to 75 wt.% of ethanol, based on the total weight of the feed.
  • the feed comprises at least 15 wt.% of acetaldehyde, preferably comprises 20 to 35 wt.% of acetaldehyde, based on the total weight of the feed.
  • the molar ratio of ethanol to acetaldehyde in the feed is in a range of from 1 to 7, preferably of from 1 .5 to 5, more preferably of from 1 .7 to 4, most preferably of from 2.0 to 3.0.
  • Preferred in terms of sodium and aluminium contents of the supported oxide catalyst according to the first aspect of the present invention correspond to preferred embodiments regarding Catalyst [M]LL and Catalyst [M]UL.
  • the support impregnated in step (i) of the process according to the invention comprises one or more of ordered and non-ordered porous silica, other porous oxides and mixtures thereof, preferably from ZrC>2, TiC>2, MgO, ZnO, NiO, and CeC>2.
  • the support impregnated in step (i) of the process according to the invention is a silica support, preferably an ordered or non-ordered porous silica support.
  • the supported oxide catalyst is a silica supported oxide catalyst and the method comprises or consists of:
  • step (vii) optionally adjusting the pH of the washed hydrogel beads obtained in step (vi), preferably to a pH in a range of about 3 to 10, most preferably to a pH of about 9, (viii) drying the washed hydrogel beads obtained in step (vi) or (vii) to obtain a silica support, preferably by using an oven,
  • step (ix) optionally, sieving of the silica support obtained in step (viii) (to collect the desired particle size fraction),
  • a “supported tantalum catalyst precursor” refers to an intermediate product, e.g., before calcination.
  • a “tantalum-containing supported oxide catalyst” is the product after calcination.
  • temperature T2 in the process according to the invention is in a range of from 40 to 130 °C.
  • the present invention relates to the use of the supported oxide catalyst according to the first aspect of the invention for the production of 1 ,3-butadiene from a feed comprising ethanol and acetaldehyde, preferably for increasing the 1 ,3-butadiene yield.
  • a dilute sodium silicate solution of 3.3 weight ratio SiO2:Na2O was reacted with dilute sulfuric acid, to form a hydrosol having the following composition: 12 wt.% SiC>2 and H2SO4:Na2O in a molar ratio of 0.8.
  • the resulting hydrosol was basic.
  • the hydrosol was then sprayed into air, where it broke into droplets and solidified into beads having a diameter of several millimeters before it was caught in a sulfuric acid solution, such that the pH of the bead/solution system was less than 2.0.
  • the beads were then washed with acidified deionized water having a pH of about 3, followed by deionized water. Then, the pH of the bead/solution system was raised to a range of 8 to 9, by adding aqueous ammonia.
  • the beads used in the comparative example were then aged at 70°C. For the inventive example, beads were aged at 125°C using Parr bombs. Aging time for both samples was ⁇ 16 hours.
  • the washed and aged hydrogel beads contain about 15-18 % SiC>2 and are at a pH of 8-9. Once washed, the pH of the beads was increased to about 9 using ammonium hydroxide solution. The beads were then dried using an oven. Finally, the beads were sieved to get the desired particle size fraction. Note that pH adjustment before drying is optional, and beads are typically dried from pH 3-9.
  • the silica gel beads with a size 2-5 mm were pre-dried to a loss of drying (LOD) ⁇ 0.5 wt.%, measured at 120 °C, before use.
  • LOD loss of drying
  • the tantalum precursor was added to the silica via the incipient wetness impregnation method.
  • a stabilized tantalum precursor solution was made by mixing approximately 5-6 g of tantalum precursor, such as 5.7 g tantalum ethoxide with 2-3 g, such as 2.8 g of 2,4-pentanedione (acetyl acetone).
  • tantalum precursor such as 5.7 g tantalum ethoxide
  • 2-3 g such as 2.8 g of 2,4-pentanedione (acetyl acetone).
  • 8.5 g of the stabilized tantalum precursor solution was dissolved in 65-76 g isopropanol, which was then added on to the pre-dried silica gel beads.
  • the amount of isopropanol was adjusted based on the support pore volume, so that the solution was contained only in the silica pores, and there was no free solution outside the pores. Impregnation took around 15-40 minutes.
  • the impregnated silica gel was kept in a sealed container for at least 1 hour before the solvent was evaporated by heating at atmospheric pressure or under vacuum. The dried material was then calcined up to 550 °C for 4 hours in air to give the finished supported oxide catalyst with approximately 3.0 wt.% Ta2C>5.
  • the levels of sodium and aluminium in the supported oxide catalyst were measured by Atomic Absorption Spectroscopy (AA) using a Perkin-Elmer PinAAcleTM 900F Spectrometer and Inductively Coupled Plasma (“ICP”) Spectroscopy using a Perkin Elmer Optima 8300 ICP-OES spectrometer, respectively.
  • Samples of supported oxide catalyst were digested with hydrofluoric acid (HF).
  • HF4 hydrofluoric acid
  • SiF4 silicon tetrafluoride
  • Sodium and aluminium levels are reported as the parts per million of the supported oxide catalyst after drying at 120 °C.
  • the sodium and aluminium amounts of the support and the tantalum starting material, respectively, can be determined accordingly if desired.
  • the levels of tantalum in the supported oxide catalyst were measured by Inductively Coupled Plasma (“ICP”) Spectroscopy using a Perkin Elmer Optima 8300 ICP-OES spectrometer. Samples of supported oxide catalyst were digested with hydrofluoric acid (HF). The resulting silicon tetrafluoride (SiF4) was fumed away and the residue was analyzed for tantalum. Results are reported on dried weight basis of the supported oxide catalyst calcined at 500 to 550 °C.
  • ICP Inductively Coupled Plasma
  • Table 1 Physico-chemical properties of the supported oxide catalysts synthesized according to the above procedure.
  • Commercial support material CARiACT Q10 from Fuji Silysia Chemical, Ltd., not prepared according to the above support preparation procedure
  • no elemental analysis performed on the as-prepared tantalum catalyst two samples measured. 2 Dry Basis.
  • the reaction was then carried out using 94 wt.% aqueous ethanol mixed with acetaldehyde at a mass ratio of 2.5:1 as feed (the mass portion of 2.5 for the 94 wt.% aqueous ethanol relates to the combined weight of water and ethanol), in the presence of nitrogen flow (200 ml/min), with a weight hourly space velocity (WHSV) of 1 .0 tr 1 and at a pressure 1 .5 barg.
  • WHSV weight hourly space velocity
  • the composition of the effluent was regularly monitored by an online gas chromatograph equipped with a flame-ionization detector coupled with a mass spectrometer (GC/MS).

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

Abstract

La présente invention concerne un catalyseur d'oxyde supporté comprenant du tantale en une quantité comprise entre 0,1 et 10 % en poids, calculée en tant que Ta2O5 et basée sur le poids total du catalyseur à base d'oxyde supporté, le catalyseur à base d'oxyde supporté présentant un diamètre moyen des pores compris entre 180 et 245 Å. De plus, l'invention concerne un tube de réaction à catalyseur pour la production de 1,3-butadiène comprenant au moins un garnissage du catalyseur à base d'oxyde supporté tel que défini dans la présente invention, un réacteur à lit fixe pour la production de 1,3-butadiène comprenant un ou plusieurs des tubes de réaction à catalyseur tels que définis dans la présente invention, et une installation pour la production de 1,3-butadiène comprenant un ou plusieurs des réacteurs à lit fixe tels que définis dans la présente invention. L'invention concerne également un procédé de production de 1,3-butadiène tel que défini dans la présente invention et un procédé de production du catalyseur supporté tel que défini dans la présente invention.
PCT/EP2025/053271 2024-02-07 2025-02-07 Catalyseur à base d'oxyde supporté comprenant du tantale avec un rendement élevé dans la production de 1,3-butadiène Pending WO2025168783A1 (fr)

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EP24461526 2024-02-07
EP24461526.6 2024-02-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180200694A1 (en) * 2015-07-13 2018-07-19 IFP Energies Nouvelles Mesoporous mixed oxide catalyst comprising silicon
US20180208522A1 (en) 2015-07-13 2018-07-26 IFP Energies Nouvelles Tantalum-based catalyst deposited on silica for the transformation of ethanol into butadiene
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