WO2015026234A1 - Catalyseur à base de nanoparticules de métal sur support pour l'hydrogénation d'une source d'acide lévulinique - Google Patents

Catalyseur à base de nanoparticules de métal sur support pour l'hydrogénation d'une source d'acide lévulinique Download PDF

Info

Publication number
WO2015026234A1
WO2015026234A1 PCT/NL2014/050569 NL2014050569W WO2015026234A1 WO 2015026234 A1 WO2015026234 A1 WO 2015026234A1 NL 2014050569 W NL2014050569 W NL 2014050569W WO 2015026234 A1 WO2015026234 A1 WO 2015026234A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
support
catalyst
oxide
ruthenium
Prior art date
Application number
PCT/NL2014/050569
Other languages
English (en)
Inventor
Sankar Meenakshisundaram
Wenhao LUO
Pieter Cornelis Antonius BRUIJNINCX
Bert Marc Weckhuysen
Original Assignee
Universiteit Utrecht Holding B.V.
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 Universiteit Utrecht Holding B.V. filed Critical Universiteit Utrecht Holding B.V.
Publication of WO2015026234A1 publication Critical patent/WO2015026234A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • 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
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite 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
    • B01J35/613—10-100 m2/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • 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

Definitions

  • the invention relates to a method for preparing a chemical compound from a levulinic acid source.
  • LA Levulinic acid
  • VDL gamma-valerolactone
  • MTHF methyltetrahydrofuran
  • PA pentanoic acid
  • PD pentanediol
  • PE pentanoic acid ester
  • WO -A- 2006/067171 relates to a process for the hydrogenation of a lactone, a carboxylic acid ester or a carboxylic acid, for example LA, in the presence of a bifunctional heterogeneous catalyst comprising (i) a zeolite or another strongly acidic component and (ii) a hydrogenating metal component.
  • a bifunctional heterogeneous catalyst comprising (i) a zeolite or another strongly acidic component and (ii) a hydrogenating metal component.
  • a catalyst useful in catalysing a conversion of a levulinic acid source into another useful chemical compound, such as GVL in particular a catalyst that is advantageous in one or more of the following aspects: catalytic activity, catalytic selectivity towards a specific useful compound of interest, catalytic productivity, robustness under reaction conditions (resistance to leaching or sintering).
  • a specific group of catalysts display a satisfactory activity, selectivity and/or productivity for a prolonged period of time in a method for converting a levulinic acid source into another useful compound, such as GVL. More in particular the inventors found that such catalysts are preparable by a specific method.
  • the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydride, levulinic acid salts, levulinic acid esters and levulinic acid amides, to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal catalyst on a support is obtainable by a metal-ion wet-impregnation method, preferably an anion-excess wet-impregnation method and wherein the metal comprises ruthenium.
  • a levulinic acid source preferably a compound selected from the group of levulinic acid, levulinic acid anhydride, levulinic acid salts, levulinic acid esters and levulinic acid amides
  • a metal catalyst on a support is obtainable by a metal-ion wet-impregnation method, preferably an anion-excess
  • the invention relates to a method for preparing a chemical compound, comprising subjecting a levulinic acid source, preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides to a reduction reaction catalysed by a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium.
  • a levulinic acid source preferably a compound selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides
  • a metal catalyst on an oxide support wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and
  • the invention relates to a metal catalyst on an oxide support, in particular a metal oxide support or a silica support, wherein the metal comprises ruthenium and wherein the catalyst is obtainable by an anion excess wet- impregnation method.
  • the invention relates to a metal catalyst on an oxide support, wherein the metal is a metal alloy of ruthenium and at least one metal selected from the group of platinum and palladium, preferably a metal alloy of ruthenium and palladium. In particular good results have been achieved with a metal alloy of ruthenium and palladium on an titanium oxide support.
  • the invention relates to a method for preparing a metal catalyst on an oxide support (for use in a method) according to the invention, comprising
  • a impregnation solution comprising a precursor for the metal catalyst - i.e. metal ions, including ruthenium ions, plus counter- anions for the metal ions (in an amount sufficient to maintain the electrochemical balance of the precursor) and an additional source of anions, i.e. the excess anions (together with counter-cations in an amount to maintain the electrochemical balance of the additional source of anions);
  • an oxide support in particular a metal oxide support or a silica support
  • a catalyst prepared according to the method of the invention has properties that are different from known catalysts, also if the known catalyst is made of the same catalytic metal and the same type of support material.
  • a catalyst according to the invention is particularly
  • the catalyst has a productivity of at least 10 molcvL . gmetai " 1 . hr 1 , preferably of at least 15 molcvL . gmetai 1 . hr 1 , more preferably of at least 25 molcvL . gmetai 1 . hr 1 , and even more preferably of at least 35 molcvL . gmetai 1 . hr 1 .
  • the productivity usually is less than 250 molcvL . gmetai 1 . hr 1 , preferably 150 molcvL . gmetai 1 . hr 1 or less, more preferably 75 molcvL .
  • gmetai 1 . hr 1 or less even more preferably 55 molcvL . gmetai 1 . hr 1 or less, in particular 25 molcvL . gmetai " 1 . hr 1 or less, more in particular 20 molcvL . gmetai "1 . hr 1 or less .
  • the productivity can be calculated by determining the moles of GVL produced (by means of GC analysis of samples taken from the reactor and quantification with an internal standard) as a function of time and divided by the grams of catalyst added to the reaction under the following conditions: reaction in liquid phase (dioxane), initially 10 wt.% LA (based on the weight of LA+dioxane), 1 wt.% (total) metal based on the weight of the metal catalyst including support, 473 K, 40 bar Lb.
  • the invention is in particular advantageous in that it allows the essentially complete (e.g. > 99 wt.%) conversion of an LA source, in particular LA, to a desired product, in particular GVL, without noticeable degradation of LA source, in particular without noticeable decarboxylation of LA or further hydrogenation of GVL.
  • Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to the invention.
  • Figure 2 shows the production of GVL during the hydrogenation of LA using monometallic 1% Ru/Ti02 (Ru, ⁇ ) made with a metal ion impregnation method with anion excess and a bimetallic 1% Ru-Pd/Ti02 (RuPd, A) made with a metal ion impregnation method with anion excess.
  • Figure 3 shows a comparison of particle sizes for the fresh and spent Ru, Pd, Ru-Pd, catalysts made with anion excess using TEM.
  • Figure 4 shows the recyclability of bimetallic RuPd/Ti02 catalyst. Recyclability tests were performed at different LA conversion levels and GVL selectivities.
  • the metal catalyst on the support is abbreviated herein after as “the metal catalyst”.
  • metal is generally used herein in a strict sense, namely to refer to the metallic form of one or more elements, unless specified or evident otherwise (e.g. when referring to metal ions or to a metal salt).
  • metal catalyst is used for a catalyst that comprises at least one catalytically active metallic element (characteristically ruthenium).
  • a specific form of a metal is an alloy.
  • substantially(ly) or “essential(ly)” is generally used herein to indicate that it has the general character, appearance or function of that which is specified. When referring to a quantifiable feature, these terms are in particular used to indicate that it is for more than 50 %, in particular at least 75 %, more in particular at least 90 %, even more in particular at least 95 % of the maximum that feature.
  • phrases "essentially consisting" of a substance (e.g. a metal) as used herein, in general means that other components than said substance are not detectible or present at a level that is generally considered an impurity.
  • "essentially consisting of means for more that 98 wt.%, more in particular for more than 99 wt.%, more in particular for more than 99.5 wt.%.
  • the term "catalytic activity" is defined (calculated) as the initial reaction rate per unit mass of catalyst. In practice this is determined by determining the (slope of concentration of LA-source vs time graph at short reaction times/time derivative of the LA-source concentration at short reaction times) divided by the grams of metal added to the reaction. A short reaction time depends on the reaction conditions and typically reflects the time wherein the first 10 mol.% or less of the initially present LA-source are converted.
  • the phrase "catalytic selectivity towards a specific useful compound” is defined (calculated) as ratio of the molar amount of the reactant (LA-source) converted to said compound (e.g. GVL) relative to the total molar amount of converted reactant (LA-source).
  • the term “catalytic productivity” is defined (calculated) as moles of desired product (e.g. GVL) per gram of metal per unit of time.
  • Resistance to leaching can be determined by determining the concentration of metal in the liquid phase after set reaction time, e.g. an hour, a day or a week.
  • the metal concentration can be determined by inductively coupled plasma mass spectrometry (ICP-MS) or inductively coupled plasma optical emission spectroscopy (ICP-OES).
  • reaction conditions of the method for preparing the chemical compound from a levulinic acid source can be chosen dependent on the compound of interest, the levulinic acid source, the information disclosed herein, the cited prior art and references cited therein, common general knowledge and optionally a limited amount of testing.
  • the LA source is selected from the group of levulinic acid, levulinic acid anhydrides, levulinic acid salts, levulinc acid esters and levulinic acid amides.
  • Angelica lactone is a preferred LA lactone. In particular, good results have been achieved with levulinic acid.
  • the reduction reaction for converting the LA source preferably is a hydrogenation reaction.
  • Suitable reducing agents are preferably selected from the group of hydrogen, formic acid and formate salts, in particular a formate salt of formate and a monovalent cation, such as ammonium formate or sodium formate.
  • GVL is formed in the hydrogenation reaction.
  • reaction conditions for the hydrogenation reaction can be based on common general knowledge and the information provided in the present disclosure.
  • GVL is usually prepared at a temperature in the range of
  • 25-250 °C preferably at a temperature in the range of 120-230 °C, and more preferably at a temperature in the range of 180-220 °C.
  • GVL is usually prepared at a hydrogen pressure of 1-100 bar, preferably of 20-70 bar, in particular of 40-50 bar.
  • the molar ratio of formate to the LA-source is typically at least about 1.
  • the formate can be applied in any excess, but usually the ratio of formate to the LA-source is 1000 or less, in particular 100 or less, and more in particular 10 or less.
  • the amount of catalyst can be chosen based on common general knowledge, depending on the type of reactor system.
  • the GVL prepared in accordance with the invention can be used in the preparation of another compound.
  • the GVL is subjected to a an acid or base catalysed ring-opening reaction to produce a mixture of pentenoic acids.
  • the GVL is subjected to an acid or base- catalysed ring-opening reaction in the presence of an alcohol to produce a mixture of alkyl pentenoates, preferably methyl pentenoates.
  • the GVL is subjected to an acid or base- catalysed ring-opening in the presence of ammonia to produce a mixture of pentenenitriles.
  • the double bond can be in the 2-, the 3- or the 4- position.
  • the double bond may be cis or trans.
  • These ring opening reactions can be advantageously performed in the gas phase or in the liquid phase. In the latter case the ring-opening reaction can advantageously be executed as a reactive distillation.
  • the GVL is subjected to an acid or base- catalyzed reaction with an aldehyde to form an alpha-alkylidene-gamma- valerolactone.
  • the aldehyde used is formaldehyde which when used in the reaction forms alpha-methylene-gamma-valerolactone.
  • the GVL is subjected to a reaction with ammonia or an N-alkylamine to form 5-methyl-pyrrolidinone or N- alkyl- 5-methyl- pyrrolidinone.
  • the N-alkylamine used is methylamine, which when used in the reaction forms N-methyl-5-methyl-pyrrolidinone.
  • the GVL is hydrogenated to form 1,5- pentanediol.
  • the GVL is hydrogenated to form 2- methyltetrahydrofuran.
  • the GVL is hydrogenated to form pentanoic acid.
  • the LA-source is converted into a salt of 4- hydroxypentanoic acid or 4-hydroxypentanamide.
  • the invention relates to the use of gamma- valerolactone prepared in accordance with the invention in the production of a fuel; a monomer, in particular a monomer for the production of a poly amide; or a solvent.
  • GVL can be converted into methyltetrahydrofuran which is suitable for use as a solvent or a fuel.
  • the catalyst of the invention comprises ruthenium and optionally one or more other metals.
  • the metal essentially consists of ruthenium.
  • ruthenium Such a catalyst, in particular when obtained by an anion excess impregnation method, has been found to be advantageously suitable for converting an LA source to GVL due to its high catalytic activity and high selectivity towards GVL.
  • the metal catalyst comprises ruthenium and at least one other metal, preferably palladium or platinum.
  • Ruthenium and the other metal(s) preferably form an alloy.
  • a preferred alloy essentially consists of ruthenium and at least one of palladium and platinum.
  • the molar ratio of the total of the metals other than ruthenium (such as palladium or platinum) to ruthenium in this embodiment can be chosen within wide limits, usually in the range of 1:99 to 90: 10, in particular in the range of 5:95 to 80:20, and more in particular in the range of 20:80 to 70:30. If palladium is present, the ratio of palladium to ruthenium is preferably at least 10:90, in particular at least 30:70, and more in particular at least 40:60. In general, the higher the palladium content, the longer the catalyst maintains a satisfactory selectivity towards GVL.
  • the total metal concentration usually is in the range of 0.1-10 wt.%, in particular in the range of 0.5- 5 wt.%.
  • the metal catalyst usually contains at least 0.1 wt.% ruthenium, based on the total weight of metal(s) and support, preferably at least 0.3 wt.% ruthenium, in particular at least 0.5 wt.% ruthenium.
  • the ruthenium content of the metal catalyst, based on the total weight of metal(s) and support usually is less than 10 wt.%, preferably 5 wt.% or less, in particular 2 wt.% or less.
  • the support preferably is a non-acidic or weakly acidic oxide.
  • a weakly acidic support is in particular a support having an isoelectric point at a
  • IEP temperature of 25 °C
  • the IEP of the support usually is 14 or less.
  • the highly acidic metal oxide WO3 typically has an IEP of 0.2- 0.5.
  • S1O2 has a lower acidity, its IEP typically being in the range of 1.7-3.5.
  • the IEP typically is 4- 11, for Ti0 2 it typically is 3.9-8.2.
  • the IEP of MgO is 12- 13. IEPs of many oxides are readily available in the art (Marek
  • Silica (S1O2) is a preferred non-metal oxide support for a metal catalyst of the invention. It has advantageous processing properties, such as pelletizing properties.
  • the supported metal catalyst is in the form of a pellet, and preferably comprises a metal catalyst on a silica support.
  • Titanium oxide and zirconium oxide are preferred metal oxide support materials.
  • the oxide may be synthetic or a natural mineral.
  • the titanium oxide comprises anatase or rutile.
  • good results have been achieved with a support comprising both anatase and rutile (70- 80 wt.% anatase and 30-20 wt.% rutile).
  • a support is commercially available from Evonik (P25-Ti0 2 )
  • Non-acidic support material is magnesium oxide.
  • the size of the support material is not critical. Usually, when preparing the catalyst on support a particulate support is provided, such as a powder. In an advantageous embodiment for the preparation of the catalyst, the particles are microp articles (particles typically having a size ⁇ 1 mm, in particular in the range of 1-200 micrometer). After the catalyst has been prepared, it may be used as such or may be shaped in a desired form, e.g. pelletized.
  • the metal catalyst on the support i.e. including support
  • the BET surface is at least 40 m 2 /g.
  • the BET surface is 800 m 2 /g or less, in particular 400 m 2 /g or less, more in particular 200 m 2 /g or less. In an embodiment, the BET surface is 75 m 2 /g or less, and in particular 60 m 2 /g or less.
  • BET advantageously is in the range of 20-75 m 2 /g, in particular in the range of 40-60 m 2 /g.
  • BET advantageously is in the range of 50- 150 m 2 /g, in particular in the range of 75- 125 m 2 /g.
  • BET usually is in the range of 50-800 m 2 /g, in particular in the range of 50-400 m 2 /g.
  • the metal on the support is present on the support surface in the form of nanop articles (particles with a size of typically less than 100 nm), and in particular in the form of metal clusters, deposited on the support.
  • These metal clusters preferably have a particle size, as determined by TEM in the range of 0.5 to 10 nm.
  • a metal catalyst obtainable in accordance with the invention is characterisable by a relatively high abundance of metal clusters present on the support, more preferably clusters having a size of about 0.5 to 5 nm and/or a relatively low polydispersity with respect to the particle size distribution of the metal nano- particles.
  • Chloride is in particular considered favourable for realising a random alloy formation.
  • the metal-alloy is characterisable by an essentially homogeneous distribution of ruthenium and the other metal(s), in particular a random alloy structure, rather than e.g. a core-shell alloy which one would expect to perform differently.
  • a homogeneous distribution and random alloy structure is determinable by XAFS or STEM, as illustrated by Figure 1. It has further been found that a metal catalyst wherein the metal is a metal alloy, in particular an alloy of ruthenium and palladium, the particle size stability of the metal particles is improved, compared to particles of a single metal, such as only ruthenium or only palladium.
  • an a impregnation solution comprising a precursor for the metal catalyst.
  • the liquid phase is usually a highly polar solvent, such as an aqueous liquid.
  • highly polar means” having about the same polarity as water or a higher polarity than water.
  • the metal precursor such as the ruthenium precursor respectively the palladium precursor, usually is a metal salt dissolved in water or an aqueous liquid.
  • metal salts are halogen salts (chloride, fluoride, iodide and bromide) and organic acid salts. Good results have been achieved with a chloride salt. Chloride has been found in particular to contribute to providing a catalyst with good catalytic properties.
  • the impregnation solution is essentially free (less than 1 wt.%) of nitrates and/or sulphates.
  • the total concentration of the metal ions is usually in the range of 1 mg metal ions/mL to 100 mg metal ions 1/mL, preferably in the range of 5 mg metal ions/mL to 10 mg metal ions /mL.
  • the impregnation solution preferably comprises an additional source of anions, in addition to the anions from the salt serving as the source for the metal ions which serve as the precursor for the catalytic metal and may be selected from the group of acids and salts of anions with volatile bases, in particular from the group of HC1, organic acids, ammonium chloride and salts of ammonium and an organic acid.
  • an impregnation solution is used is called an anion excess
  • the concentration of the acid or salt of the anions and a volatile base preferably is 10- 100 mL of a 0.1-10 M solution, in particular 15-30 mL of a 0.1 to 5 M solution, per 0.5 to 5 gram support.
  • the impregnation may be carried out in a manner known per se.
  • the support is advantageously mixed with the impregnation solution by agitation, for instance by vigorous stirring, e.g. using a magnetic bar/stirrer set-up above 900 rpm, whereby the mixing of support and impregnation liquid is effected.
  • the impregnation can be carried out at any temperature between the melting point and the boiling point of the liquid phase, and is advantageously carried out at ambient temperature, e.g. at about 25 °C.
  • the temperature is preferably raised to about 50-90 °C. This will allow evaporation of the solvent at a desired evaporation rate.
  • the drying may be carried out in a manner known per se. In particular good results have been achieved with a method wherein the slurry of support in the impregnation solution is dried in hot open air atmosphere typically at a
  • the drying is preferably carried out whilst agitating the slurry, for instance by stirring or drying in a fluidized bed.
  • the agitation is preferably vigorous enough to achieve intensive mixing of the contents of the slurry.
  • the drying is usually continued until a visually dry product is obtained.
  • the drying usually takes 24 hours or less, in particular 1-20 hours, more in particular 5-20 hours.
  • the dried product is ground, prior to reduction.
  • the dried impregnated oxide support is reduced without first having been subjected to a calcination step.
  • the catalyst is a non-calcined catalyst.
  • calcination is generally known as a heat treatment of a catalyst precursor in an oxidizing atmosphere (of variable composition) for variable amount of time and at a temperature sufficient to convert essentially all precursors into oxides, i.e. to remove essentially all anions except oxygen as well as any solvent molecules.
  • Reducing is preferably carried out using hydrogen, for instance 1-10 vol.% hydrogen in an inert gas, such as nitrogen, argon and/or helium.
  • the reduction is preferably carried out at a temperature in the range of 250 °C to 600 °C.
  • the temperature is gradually raised until the desired maximum temperature is reached, in particular at a ramp-rate in the range of 1-5 °C/min.
  • an advantageous balance is reached between removing the anions, such as chloride ions, increasing the metal-support interaction and preventing the metal particles from sintering.
  • a slower rate of ramping typically increases the dispersion of the metal particles within the catalyst.
  • the reduction is preferably carried out for a period of at least 1 h, in particular for a period of 2 h to 10 h.
  • RuC (Acros Chemicals) was used as the ruthenium precursor and was dissolved in deionized water to form an aqueous precursor solution with a ruthenium concentration of 5.28 mg / mL.
  • the requisite amount of the precursor solution (1.89 mL for preparing a 1 wt.% Ru catalyst on support) was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of
  • the slurry was stirred vigorously at 298 K for about 30 min and then the oil bath temperature was raised to 333 K, stirred for 1 h and then finally heated to 358 K. The slurry was stirred at this temperature overnight until all the water had evaporated.
  • the solid powder denoted as the "dried sample” was ground thoroughly with a mortar and pestle and approximately 350 mg of this material was then reduced in a furnace at 723 K (approx. 2 K / min ramp rate) under a flow of 5 vol.% Lb / N2 (total flow: 420 mL/min ) for 4 h, without having been subjected to a calcination step. Finally the furnace was cooled rapidly to room temperature and the catalyst sample was used without any further modification.
  • the resultant catalyst contained a 1 wt.% metal (Ru) concentration on a 1 g production scale.
  • Reactions were performed with 10 wt.% levulinic acid (6.0 g, 51.7 mmol) in dioxane (54 g) with 1 wt.% catalyst (0.6 g).
  • the reactions were run in a 100 mL Parr batch autoclave at a temperature of 473 K using a hydrogen pressure of 40 bar and a stirring speed of 1600 rpm.
  • the batch autoclave reactor was loaded with catalyst, substrate and solvent, purged three times with argon after which the reaction mixture was heated to reaction temperature and charged with Lb to 40 bar. 1 mL of solution was sampled at various intervals during the reaction.
  • the autoclave was cooled to room temperature, the Lb was released and 2 wt.% anisole was added as an internal standard.
  • the catalyst was separated by filtration and washed with acetone.
  • reaction products were analyzed using a Shimadzu GC-2010A gas chromatograph equipped with a CP-WAX 57-CB column (25 m x 0.2 mm x 0.2 ⁇ ) and FID detector. Products were identified with a GC-MS from Shimadzu with a CP-WAX 57CB column (30 m x 0.2 mm x 0.2 ⁇ ). Results
  • the activity and selectivity of supported monometal Ru catalyst was found to be strongly influenced by both its preparation method and by alloying it with a second metal, such as Pd.
  • the Ru catalyst according to the invention gave full conversion after 40 min with 99.0 mol.% selectivity to GVL (0.1 mol.% MTHF and 0.1 mol.% PD as a byproduct); cf. 43.3 mol.% conversion after 40 min for the comparative Ru catalyst (WI), and 99.5 mol.% selectivity to GVL.
  • the productivity of the Ru/Ti02 catalyst according to the invention was 16.4 molcvL . g metai 1 . hr 1 , thus outperforming the catalysts listed in a recent LA hydrogenation review paper (Wright, W.R.H. et al. ChemSusChem 5 (2012) 1657- 1667).
  • This Ru/Ti02 catalyst according to the invention was very active and gave excellent selectivity at short reaction times of 40 min. At longer reaction times, however, consecutive reactions took place causing a drop in selectivity and mass balance after 2 h (selectivity: 93.0 mol.% GVL, 1.2 mol.% PD, 0.7 mol.% MTHF).
  • the catalyst according to the invention showed very limited leaching (i.e. loss of 0.5 wt.% loss of the total amount of ruthenium originally present after 10 h in neat LA) and very limited sintering was observed.
  • PdC salt (Sigma Aldrich) was dissolved in deionized water to form an aqueous precursor solution with a resultant palladium concentration of 3.02 mg / mL. This solution was slowly cooled and used as the palladium precursor solution. This solution was used together with the Ru precursor solution of Example 1 in amounts to provide a molar ratio of Ru:Pd of 1:1. The requisite amount of the precursor solution was charged in to a clean 50 mL round bottomed flask fitted with a magnetic stirrer, after which the requisite amount of concentrated HCl
  • Example 1 A RuPd on Ti02 catalyst was obtained, comprising 1 wt.% of the Ru-Pd alloy (molar ratio Ru:Pd 1: 1).
  • the Ru-Pd metal alloy catalyst was found to have a high activity (i.e. full conversion after 30 min, 99.6 mol.% selectivity to GVL, 0.1 mol.% PD, 0.3 mol.% MTHF; note that this is at only 0.49 wt.% Ru metal loading), and stayed completely selective also at longer reaction times (1 h, sel. 99.2 mol.% GVL, 0.2 mol.% PD, 0.4 mol.% MTHF, 0.1 mol.% PA)
  • the productivity of the RuPd/Ti0 2 catalyst was 17.2 molcvL . gmetai 1 . hr 1 .
  • This catalyst was also compared with a catalyst, prepared with the same method as described in Example 1, except that all Ru was replaced by Pd.
  • This Pd/Ti02 catalyst shows negligible activity with respect to the conversion of levulinic acid. Characterization of the catalyst
  • Figure 1 shows a STEM - EDX mapping of a RuPd catalyst prepared according to Example 2 (molar ratio of Ru:Pd of 1: 1). Details about the mapping can be found in "Aberration Corrected Analytical Electron Microscopy Studies Of Bimetallic Nanopar tides", A.A. Herzing, M.Watanabe, C.J.Kiely, J.Edwards,
  • the images are STEM high angle annular dark field (HAADF) images of the metallic particles obtained using an aberration corrected JEM ARM-200F STEM operating at 200 kV.
  • XEDS X-ray energy dispersive
  • Figure-2 shows that the GVL yield (A), was stable for several hours even after reaching quantitative conversion when the bimetallic catalyst was used.
  • the GVL yield started to drop after reaching a maximum of 99.0%. This is because of the further hydrogenation of the product GVL to 1,4-pentanediol (PD) and
  • MTHF methyltetrahydrofuran
  • Figure -3 shows the results from the TEM measurements of the metal particle sizes for the fresh (white bars) and spent (grey bars) monometallic (Ru or Pd) and bimetallic (Ru-Pd) catalysts, made with a method of the invention. From the figure it is evident that the metal particle sizes increased when the monometallic catalysts were used once. However, the particle sizes remained the same for the bimetallic catalysts even after 3 runs (grey, hatched bar). This shows that alloying Pd with Ru substantially helps in stabilizing the small particle for several cycles. This stability of the small particles, in the case of bimetallic catalysts, resulted in the catalytic activity of the recovered catalysts.
  • Figure-4 shows the catalytic activity of the fresh and recovered bimetallic catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un composé chimique, comprenant la soumission d'une source d'acide lévulinique, de préférence un composé choisi dans le groupe de l'acide lévulinique, des anhydrides d'acide lévulinique, des sels d'acide lévulinique, des esters d'acide lévulinique et des amide d'acide lévulinique à une réaction de réduction catalysée par un catalyseur métallique sur un support d'oxyde, le catalyseur métallique sur support pouvant être obtenu par un procédé d'imprégnation d'ions métalliques, ledit procédé d'imprégnation d'ions métalliques utilisant un excès d'anions, et le métal comprenant du ruthénium, en particulier du ruthénium et du palladium.
PCT/NL2014/050569 2013-08-20 2014-08-20 Catalyseur à base de nanoparticules de métal sur support pour l'hydrogénation d'une source d'acide lévulinique WO2015026234A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13181028.5 2013-08-20
EP13181028 2013-08-20

Publications (1)

Publication Number Publication Date
WO2015026234A1 true WO2015026234A1 (fr) 2015-02-26

Family

ID=48986050

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NL2014/050569 WO2015026234A1 (fr) 2013-08-20 2014-08-20 Catalyseur à base de nanoparticules de métal sur support pour l'hydrogénation d'une source d'acide lévulinique

Country Status (1)

Country Link
WO (1) WO2015026234A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106349014A (zh) * 2016-08-23 2017-01-25 上海交通大学 利用乙酰丙酸酯制备1,4‑戊二醇的方法
WO2017085986A1 (fr) * 2015-11-16 2017-05-26 宇部興産株式会社 Procédé de production de γ-valérolactone
US9878967B2 (en) 2015-12-23 2018-01-30 Iowa State University Research Foundation, Inc. Method of converting levulinic acid or a derivative thereof to hydrocarbons and hydrogen, and methods of the production of hydrocarbons and hydrogen
CN107824180A (zh) * 2017-08-25 2018-03-23 昆山普瑞凯纳米技术有限公司 一种用于乙酰丙酸加氢的负载型纳米金属催化剂的制备方法
CN110615754A (zh) * 2019-09-16 2019-12-27 浙江工业大学 一种5-甲基-2-吡咯烷酮的合成方法
CN114573450A (zh) * 2020-12-01 2022-06-03 中国科学院大连化学物理研究所 一种MnCeOx催化乙酰丙酸制备乙酸的方法
CN115283001A (zh) * 2022-08-22 2022-11-04 西北工业大学 一种耐高温负载型金属催化剂及其制备方法
EP4269462A1 (fr) 2022-04-26 2023-11-01 Henkel AG & Co. KGaA Composition acrylique à deux composants (2k) comprenant un polyuréthane thermoplastique
EP4269518A1 (fr) 2022-04-26 2023-11-01 Henkel AG & Co. KGaA Composition acrylique à deux composants (2k) comprenant un monomère bio-renouvelable

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006067171A1 (fr) 2004-12-23 2006-06-29 Shell Internationale Research Maatschappij B.V. Procede d'hydrogenation d'une lactone ou d'un acide carboxylique ou d'un ester comprenant un groupe gamma-carbonyle

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006067171A1 (fr) 2004-12-23 2006-06-29 Shell Internationale Research Maatschappij B.V. Procede d'hydrogenation d'une lactone ou d'un acide carboxylique ou d'un ester comprenant un groupe gamma-carbonyle

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
A.A. HERZING; M.WATANABE; C.J.KIELY; J.EDWARDS; M.CONTE; Z.R.TANG; G.J.HUTCHINGS: "Aberration Corrected Analytical Electron Microscopy Studies Of Bimetallic Nanoparticles", FARADAY DISCUSSIONS, vol. 138, 2008, pages 337 - 351
APPL. CATAL. B., vol. 117, 2012, pages 321 - 329
DEMIRCI U B ET AL: "Ru-based bimetallic alloys for hydrogen generation by hydrolysis of sodium tetrahydroborate", JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 463, no. 1-2, 8 September 2008 (2008-09-08), pages 107 - 111, XP023175991, ISSN: 0925-8388, [retrieved on 20080723], DOI: 10.1016/J.JALLCOM.2007.08.077 *
HENGNE A M ET AL: "Surface Species of Supported Ruthenium Catalysts in Selective Hydrogenation of Levulinic Esters for Bio-Refinery Application", CATALYSIS LETTERS, KLUWER ACADEMIC PUBLISHERS-PLENUM PUBLISHERS, NE, vol. 142, no. 6, 3 May 2012 (2012-05-03), pages 779 - 787, XP035059431, ISSN: 1572-879X, DOI: 10.1007/S10562-012-0822-4 *
LI DENG ET AL: "Conversion of Levulinic Acid and Formic Acid into [gamma]-Valerolactone over Heterogeneous Catalysts", CHEMSUSCHEM, vol. 3, no. 10, 25 October 2010 (2010-10-25), pages 1172 - 1175, XP055097351, ISSN: 1864-5631, DOI: 10.1002/cssc.201000163 *
LUO, W. ET AL., JOURNAL OF CATALYSIS, vol. 301, 2013, pages 175 - 186
MAREK KOSMULSKI: "Chemical Properties of Material Surfaces", 2001, MARCEL DEKKER
MEENAKSHISUNDARAM SANKAR ET AL: "Synthesis of Stable Ligand-free Gold-Palladium Nanoparticles Using a Simple Excess Anion Method", ACS NANO, vol. 6, no. 8, 28 August 2012 (2012-08-28), pages 6600 - 6613, XP055062944, ISSN: 1936-0851, DOI: 10.1021/nn302299e *
MOHAMMAD G. AL-SHAAL ET AL: "Exploring the ruthenium catalysed synthesis of [gamma]-valerolactone in alcohols and utilisation of mild solvent-free reaction conditions", GREEN CHEMISTRY, vol. 14, no. 5, 1 January 2012 (2012-01-01), pages 1260 - 1963, XP055096687, ISSN: 1463-9262, DOI: 10.1039/c2gc16631c *
TAO PAN ET AL: "Catalytic conversion of biomass-derived levulinic acid to valerate esters as oxygenated fuels using supported ruthenium catalysts", GREEN CHEMISTRY, vol. 15, no. 10, 1 January 2013 (2013-01-01), pages 2967 - 2974, XP055096685, ISSN: 1463-9262, DOI: 10.1039/c3gc40927a *
W. ZHOU; I. E. WACHS; C. J. KIELY: "Nanostructural and Chemical Characterization of Supported Metal Oxide Catalysts by Aberration Corrected Analytical Electron Macroscopy", CURRENT OPINION IN SOLID STATE AND MATERIALS SCIENCE, vol. 16, 2012, pages 10 - 22, XP028126071, DOI: doi:10.1016/j.cossms.2011.06.001
WENHAO LUO ET AL: "Ruthenium-catalyzed hydrogenation of levulinic acid: Influence of the support and solvent on catalyst selectivity and stability", JOURNAL OF CATALYSIS, vol. 301, 1 May 2013 (2013-05-01), pages 175 - 186, XP055155589, ISSN: 0021-9517, DOI: 10.1016/j.jcat.2013.02.003 *
WILLIAM R. H. WRIGHT ET AL: "Development of Heterogeneous Catalysts for the Conversion of Levulinic Acid to [gamma]-Valerolactone", CHEMSUSCHEM, vol. 5, no. 9, 13 September 2012 (2012-09-13), pages 1657 - 1667, XP055097062, ISSN: 1864-5631, DOI: 10.1002/cssc.201200111 *
WRIGHT, W.R.H. ET AL., CHEMSUSCHEM, vol. 5, 2012, pages 1657 - 1667

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017085986A1 (fr) * 2015-11-16 2017-05-26 宇部興産株式会社 Procédé de production de γ-valérolactone
JPWO2017085986A1 (ja) * 2015-11-16 2018-09-06 宇部興産株式会社 γ−バレロラクトンの製造方法
US10227318B2 (en) 2015-11-16 2019-03-12 Ube Industries, Ltd. Method for producing gamma-valerolactone
US9878967B2 (en) 2015-12-23 2018-01-30 Iowa State University Research Foundation, Inc. Method of converting levulinic acid or a derivative thereof to hydrocarbons and hydrogen, and methods of the production of hydrocarbons and hydrogen
CN106349014A (zh) * 2016-08-23 2017-01-25 上海交通大学 利用乙酰丙酸酯制备1,4‑戊二醇的方法
CN106349014B (zh) * 2016-08-23 2020-08-18 上海交通大学 利用乙酰丙酸酯制备1,4-戊二醇的方法
CN107824180A (zh) * 2017-08-25 2018-03-23 昆山普瑞凯纳米技术有限公司 一种用于乙酰丙酸加氢的负载型纳米金属催化剂的制备方法
CN110615754A (zh) * 2019-09-16 2019-12-27 浙江工业大学 一种5-甲基-2-吡咯烷酮的合成方法
CN114573450A (zh) * 2020-12-01 2022-06-03 中国科学院大连化学物理研究所 一种MnCeOx催化乙酰丙酸制备乙酸的方法
CN114573450B (zh) * 2020-12-01 2023-05-30 中国科学院大连化学物理研究所 一种MnCeOx催化乙酰丙酸制备乙酸的方法
EP4269462A1 (fr) 2022-04-26 2023-11-01 Henkel AG & Co. KGaA Composition acrylique à deux composants (2k) comprenant un polyuréthane thermoplastique
EP4269518A1 (fr) 2022-04-26 2023-11-01 Henkel AG & Co. KGaA Composition acrylique à deux composants (2k) comprenant un monomère bio-renouvelable
WO2023208579A1 (fr) 2022-04-26 2023-11-02 Henkel Ag & Co. Kgaa Composition acrylique à deux composants (2k) comprenant un polyuréthane thermoplastique
WO2023208580A1 (fr) 2022-04-26 2023-11-02 Henkel Ag & Co. Kgaa Composition acrylique à deux composants (2k) comprenant un monomère bio-renouvelable
CN115283001A (zh) * 2022-08-22 2022-11-04 西北工业大学 一种耐高温负载型金属催化剂及其制备方法
CN115283001B (zh) * 2022-08-22 2023-11-14 西北工业大学 一种耐高温负载型金属催化剂及其制备方法

Similar Documents

Publication Publication Date Title
WO2015026234A1 (fr) Catalyseur à base de nanoparticules de métal sur support pour l'hydrogénation d'une source d'acide lévulinique
US11596927B2 (en) Oxidation catalysts
AU2010355259B2 (en) Catalyst comprising platinum and gold nano - particles and its use for oxidation of glucose and preparation method of such a catalyst
Rodrigues et al. Gold supported on carbon nanotubes for the selective oxidation of glycerol
Su et al. Gold Supported on Nanocrystalline b-Ga2O3 as a Versatile Bifunctional Catalyst for Facile Oxidative Transformation of Alcohols, Aldehydes, and Acetals into Esters
JP5035790B2 (ja) プロパンジオールの製造方法
EP3647310B1 (fr) Procédé de préparation de 2,5-furandiméthylcarboxylate à partir d'hydroxyméthylfurfural
Megías-Sayago et al. Au/Al2O3–Efficient catalyst for 5-hydroxymethylfurfural oxidation to 2, 5-furandicarboxylic acid
TWI513683B (zh) Preparation of alicyclic carboxylic acids
EP3322526B1 (fr) Catalyseurs multimétalliques contenant du cuivre améliorés et procédé d'utilisation de ceux-ci pour produire du 1,2-propane-diol d'origine biologique
KR20200051803A (ko) 알데히드의 카르복실산 에스테르로의 산화적 에스테르화를 위한 촉매
WO2016135268A1 (fr) Procédé de préparation d'un composé chimique à l'aide d'un catalyseur au ruthénium métallique sur un support de zircone en présence d'un contaminant
KR20100019569A (ko) 카르복실산에스테르 제조용 촉매, 그 제조방법 및 카르복실산에스테르의 제조방법
EP2755760A1 (fr) Catalyseur pour la synthèse d'h2o2 et procédé de préparation d'un tel catalyseur
CN110382452B (zh) 羰基化合物的加氢催化剂及醇的制造方法
CN107921429B (zh) 用于制备丙烯酸的非均相催化剂和使用其制备丙烯酸的方法
EP2864280B1 (fr) Procédé de préparation d'un catalyseur supporté
CN107824180A (zh) 一种用于乙酰丙酸加氢的负载型纳米金属催化剂的制备方法
CN108137464B (zh) 制备丙烯酸的方法
JP2007275854A (ja) 反応安定性に優れたカルボン酸エステル製造用触媒及びカルボン酸エステルの製造方法
WO2019141848A1 (fr) Support de catalyseur comprenant du dioxyde de titane distribué de manière homogène et procédé de production
WO2015055942A2 (fr) Catalyseur métallique supporté et son utilisation pour l'oxydation sélective du glycérol
Hoelderich et al. Preparation of a raspberry ketone precursor in the presence of rare earth oxide catalysts
KR102537116B1 (ko) 클로로포름을 디클로로메탄으로 전환시키기 위한 탈염소수소화 촉매 및 그 제조방법, 상기 촉매를 이용하여 클로로포름을 디클로로메탄으로 전환시키는 방법
CN112469683A (zh) 醇的制造方法和催化剂

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14772227

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14772227

Country of ref document: EP

Kind code of ref document: A1