WO2020048855A1 - Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide - Google Patents

Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide Download PDF

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WO2020048855A1
WO2020048855A1 PCT/EP2019/073048 EP2019073048W WO2020048855A1 WO 2020048855 A1 WO2020048855 A1 WO 2020048855A1 EP 2019073048 W EP2019073048 W EP 2019073048W WO 2020048855 A1 WO2020048855 A1 WO 2020048855A1
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weight
liquid phase
catalyst
general formula
intermetallic compound
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PCT/EP2019/073048
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English (en)
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Michaela FENYN
Nicolas VAUTRAVERS
Joaquim Henrique Teles
Joseph John ZAKZESKI
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Basf Se
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    • 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
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups

Definitions

  • the present invention relates to a process for preparing alpha, beta unsaturated aldehydes, such as in particular, prenal (3-methyl-2-butenal) by oxidation of alcohols in the presence of a liquid phase. More specifically, the invention relates to a process for preparing alpha, beta unsaturated aldehydes, such as, in particular prenal (3-methyl-2-butenal) by oxidation of alcohols in the pres- ence of a catalyst and a liquid phase, wherein the liquid phase contains 0.1 to less than 25 weight- % water and wherein the liquid phase contains at least 25 weight-% of alcohol(s) of general for- mula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and wherein the oxidant is oxygen and/or hydrogen peroxide and wherein the catalyst comprises at least one intermetallic compound.
  • Prenal is an important chemical intermediate especially for the preparation of terpene-based fra- grances, such as citral, and for the preparation of vitamins, such as vitamin E, and therefore is of great technical and economic importance.
  • EP 0 881 206 describes the oxida- tion of these starting compounds with oxygen in the gas phase using a silver catalyst.
  • the selec- tivity of this approach could be improved by further developing the catalytic system, as disclosed e.g. in WO 2008/037693.
  • WO 99/18058 discloses a process for the aerobic oxidation of primary alcohols, such as hexanol in the absence of solvents.
  • Table 2 describes the oxida- tion of geraniol with oxygen and a Pt/Bi/C catalyst.
  • the reaction was conducted with 15 mmol reactant in 30 ml toluene, which amounts to 8,88 weight-% reactant (alcohol). At a conversion of 100% and after 6 hours, this results in a space-time-yield of 14,67 g/l/h.
  • Green Chemistry, 2 (2000) describes on page 280, table 1 entry 2 the aerobic selective oxidation of crotyl alcohol over a Pt/Bi/graphite catalyst.
  • the reaction was conducted with 5 mmol substrate in 60 ml solvent (ethanol). This amounts to 0,75 weight-% of crotyl alcohol.
  • Crotonaldehyde is obtained with a yield of 42% after 15 hours, resulting in a space-time-yield of 0,16 g/l/h.
  • Table 1 entry 7 describes the aerobic selective oxidation of trans- hex-2-en-1 -ol. The reaction was conducted with 5 mmol substrate in 60 ml solvent (ethanol). This amounts to 1 ,0 weight-% of alcohol. The aldehyde is obtained with a yield of 57% after 15 hours, resulting in a space-time-yield of 0,3 g/l/h.
  • entry 4 describes the oxidation of prenol to prenal, wherein 4,3 weight-% of alcohol is used.
  • the reaction is con- ducted for 8 hours with a conversion of 53% and a selectivity of 99%, resulting in a space-time- yield of 2,8 g/l/h.
  • Molecular Catalysis A Chemical 2010, 331 (1 -2)
  • table 4 describes the oxidation of prenol to prenal, wherein 4,3 weight% of alcohol is used.
  • the reaction is conducted for 12 hours with a conversion of 89,5% and a selectivity of 99%, resulting in a space-time-yield of 3,1 g/l/h.
  • the reaction volume is the volume of the reactor in which the reaction takes place. In case the reaction is conducted in a cylindrical reactor, the reaction volume is the volume of the cylindrical reactor in which the reaction takes place.
  • processes which allow high space-time-yields in a reaction time in which at least 40%, preferably at least 50% conversion is achieved.
  • SA specific activity
  • SA is defined as the amount of product obtained per amount of catalytically active metal per hour of reaction, ex- pressed as g/g/h.
  • processes which allow high specific activities in a reaction time in which at least 40%, preferably at least 50% conversion is achieved.
  • the objectives are achieved by an oxidation in the presence of a catalyst and in the presence of a liquid phase, wherein the liquid phase contains 0.1 to less than 25 weight-% water and wherein the liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and wherein the oxidant is oxygen and/or hydrogen peroxide, and wherein the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar.
  • the alpha, beta unsaturated aldehydes of formula (I) can be obtained with excellent yield and selectivity with the process according to the invention.
  • the pro- cess according to the invention is further associated with a series of advantages.
  • the process according to the invention enables the preparation of alpha, beta unsaturated aldehydes of for- mula (I) with high yield and high selectivity under mild conditions, both of temperature and pres- sure, while requiring only moderate to low amounts of catalyst.
  • the process can be conducted with no or low amounts of organic solvent, thus avoiding or minimizing environmentally problem- atic waste streams.
  • the process also allows a simple isolation of the desired aldehyde.
  • a further advantage of the process of the invention is that the desired aldehyde is obtained in a high con- centration in the reaction mixture, thus minimizing down-stream isolation steps.
  • the process ac- cording to the invention leads to space-time-yields, which are higher than the space-time-yields that are obtainable with processes according to the prior art.
  • specific activities can be achieved, which are higher than the specific activities that are possible with processes according to the prior art.
  • the present invention relates to a process for the preparation of alpha, beta unsatu- rated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different sub- stituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, F3 ⁇ 4 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar.
  • the prefix C x -C y denotes the number of possible carbon atoms in the particular case.
  • Ci-C 4 -alkyl denotes a linear or branched alkyl radical comprising from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 1 -methylethyl (isopropyl), butyl, 1 -methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 , 1 -dimethylethyl (tert-butyl).
  • Ci-C 6 -alkyl denotes a linear or branched alkyl radical comprising 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl, 1 ,1 -di- methylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpro- pyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpen- tyl, 4-methylpentyl, 1 , 1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl
  • alkenyl denotes mono- or poly-, in particular monounsaturated, straight-chain or branched hydrocarbon radicals having x to y carbon atoms, as denoted in C x -C y and a double bond in any desired position, e.g.
  • C2-C6-alkenyl, or C2-C4 alkenyl such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 - propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pen- tenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl- 2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1 -di- methyl-2-propenyl, 1 ,2-
  • Each double bond in the alkenyl moiety can independently of each other be present in the E- or the Z-configuration.
  • substituents denotes radicals selected from the group consisting of NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine.
  • alkoxy denotes straight-chain or branched saturated alkyl radicals comprising from 1 to 6 (Ci-C 6 -alkoxy) or 1 to 4 (Ci-C 4 -alkoxy) carbon atoms, which are bound via an oxygen atom to the remainder of the molecule, such as methoxy, ethoxy, n-propoxy, 1 -methylethoxy (isopropoxy), n-butyloxy, 1 -methylpropoxy (sec-butyloxy), 2-methylpropoxy (isobutyloxy) and 1 ,1 -dimethyleth- oxy (tert-butyloxy).
  • (Ci-C 6 -alkoxy)carbonyl denotes alkoxy radicals having from 1 to 6 carbon atoms which are bound via a carbonyl group to the remainder of the molecule. Examples thereof are methox- ycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec- butoxycarbonyl, isobutoxycarbonyl and tert-butoxycarbonyl, n-pentyloxycarbonyl and n-hex- yloxycarbonyl.
  • C1-C6 acyl denotes straight-chain or branched saturated alkyl radicals comprising from 1 to 6 carbon atoms, which are bound via a carbonyl group to the remainder of the molecule. Examples thereof are formyl, acetyl, propionyl, 2-methylpropionyl, 3-methylbutanoyl, butanoyl, pentanoyl, hexanoyl.
  • C1-C6 acyloxy denotes C1-C6 acyl radicals, which are bound via an oxygen atom to the remainder of the molecule. Examples thereof are acetoxy, propionyloxy, butanoyloxy, penta- noyloxy, hexanoyloxy.
  • aryl denotes carbocyclic aromatic radicals having from 6 to 14 carbon atoms. Examples thereof comprise phenyl, naphthyl, fluorenyl, azulenyl, anthracenyl and phenanthrenyl.
  • Aryl is preferably phenyl or naphthyl, and especially phenyl.
  • Selectivity is defined as the number of moles of the alpha, beta unsaturated aldehyde of the gen- eral formula (I) formed divided by the number of moles of the alcohol of the general formula (II) that were consumed.
  • the amounts of alpha, beta unsaturated aldehyde of the general formula (I) formed and of alcohol of the general formula (II) consumed can easily be determined by a GC analysis as defined in the experimental section.
  • Reactant(s) of the process of the invention are alcohol(s) of general formula (II) wherein Ri, R 2 and R 3 , independently of one another, are selected from
  • Ci-C 6 -alkyl which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and
  • C 2 -C 6 -alkenyl which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 - C 6 acyloxy and aryl;
  • alcohol(s) encompasses one alcohol as well as a mixture of more than one alcohol according to formula (II).
  • alcohol(s) of general formula (II) are used, wherein R 3 is H.
  • alcohol(s) of general formula (II) are used, wherein Ri, R 2 and R 3 , independently of one another, are selected from the group consisting of H, Ci-C 6 -alkyl and C 2 -C 6 -alkenyl.
  • alcohol(s) of general formula (II) are used, wherein Ri, R 2 and R 3 , independently of one another, are selected from the group consisting of H, Ci-C 6 -alkyl and C 2 -C 4 -alkenyl.
  • alcohol(s) of general formula (II) are used, wherein Ri, R 2 and R 3 , independently of one another, are selected from the group consisting of H, Ci-C 4 -alkyl and C 2 -C 6 -alkenyl.
  • alcohol(s) of general formula (II) are used, wherein Ri, R 2 and R 3 , independently of one another, are selected from the group consisting of H, Ci-C 4 -alkyl and C 2 -C 4 -alkenyl.
  • alcohol(s) of general formula (II) are used, wherein Ri, R 2 and R 3 , independently of one another, are selected from the group consisting of H, CH 3 and C 2 H 5 . In one embodiment of the invention alcohol(s) of general formula (II) are used, wherein Ri, R and R 3 , independently of one another, are selected from the group consisting of H and CH 3 .
  • an alcohol of the general formula (II) is used, wherein R is H and R and R3 are CH3.
  • an alcohol of the general formula (II) is used, wherein R is CH 3 , R 3 is H and R is C -Alkenyl, preferably 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl- 1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
  • an alcohol of the general formula (II) is used, wherein R is CH 3 , R 3 is H and R 1 is C -Alkenyl, preferably 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl- 1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
  • the alcohol of the general formula (II) is selected from the group consisting of (2E)-3,7-dimethylocta-2,6-dien-1 -ol, (2Z)-3,7-dimethylocta-2,6-dien-1 -ol, 3- methylbut-2-en-1 -ol, (E)-2-methylbut-2-en-1 -ol and (Z)-2-methylbut-2-en-1 -ol. In one embodiment of the invention the alcohol of the general formula (II) is 3-methylbut-2-en-1 - ol.
  • the invention also encom- passes the embodiment that 2-methyl-3-buten-2-ol (dimethylvinylcarbinol, DMVC) is added to the reaction and subsequently isomerized to 3-methylbut-2-en-1 -ol.
  • 2-methyl-3-buten-2-ol dimethylvinylcarbinol, DMVC
  • the alcohol of the general formula (II) is a mixture of (2E)-3,7- dimethylocta-2,6-dien-1 -ol and (2Z)-3,7-dimethylocta-2,6-dien-1 -ol.
  • Product(s) of the process of the invention are alpha, beta unsaturated aldehyde(s) of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different sub- stituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl.
  • aldehyde(s) encompasses one aldehyde as well as a mixture of more than one aldehyde according to formula (I).
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar.
  • the process according to the invention is conducted in the presence of a liquid phase.
  • the liquid phase consists of all components of the reaction which are liquid at 20 °C and a pressure of 1 bar.
  • All weight-% of the liquid phase referred to in the process according to the invention are based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar.
  • the process according to the invention is conducted in a liquid phase (catalyst and oxidant are part of the liquid phase, homogenous catalyzed pro- cess) or at the interphase between liquid phase and the solid catalyst (heterogeneous catalyzed process).
  • a liquid phase catalyst and oxidant are part of the liquid phase, homogenous catalyzed pro- cess
  • heterogeneous catalyzed process at the interphase between liquid phase and the solid catalyst.
  • the term“in the presence of a liquid phase” encompasses the process in a liquid phase as well as the process at the interphase.
  • the solid catalyst is not liquid at a temperature of 20°C and a pressure of 1 bar and is therefore by definition not included in the weight-% of the liquid phase.
  • the liquid phase can consist of one or more, e.g. two or three distinct liquid phases.
  • the number of liquid phases can be chosen by a man skilled in the art, dependent for example on the choice and concentration of the alcohol(s) of general formula (II) or on optional solvent(s).
  • the process according to the invention can be conducted in the presence of a liquid phase, which consists of one liquid phase (mono-phase system).
  • a liquid phase which consists of more than one, e.g. two, three or more distinct liquid phases (multi-phase system).
  • the liquid phase contains
  • the liquid phase contains 0.1 to less than 25 weight-% water.
  • At least one distinct liquid phase contains 0.1 to less than 25 weight-% water.
  • the man skilled in the art will choose the water content of the reaction so that it will not exceed 25 weight-% during the course of the reac- tion.
  • the following preferred ranges for the water content of a liquid phase apply for the liquid phase for mono-phase systems or for the at least one distinct liquid phase for multi-phase systems.
  • the process is performed in the presence of a liquid phase, which contains 0.5 to 20 weight-%, preferably 1.0 to 15 weight-% water based on the total weight of the liquid phase.
  • the process can be performed in the presence of a liquid phase, which contains 1.0 to 10 weight-%, preferably 1 .0 to 8 weight-%, preferably 1 .0 to 6 weight-%, preferably 1 .0 to 5 weight-%, preferably 1 .0 to 3 weight-% water based on the total weight of the liquid phase. All weight-% of water are based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the process is performed in the presence of a liquid phase, which contains 0.1 to 20 weight-%, preferably 0.1 to 10 weight-% water based on the total weight of the liquid phase. All weight-% of water are based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains at least 25 weight-% of reactant(s) and product(s).
  • At least one distinct liquid phase contains at least 25 weight-% of reactant(s) and product(s).
  • the following preferred ranges for the weight-% of reactant(s) and product(s) of a liquid phase apply for the liquid phase for mono-phase systems or for the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains at least 30 weight-%, preferably at least 50 weight-%, preferably at least 60 weight-%, preferably at least 70 weight-%, preferably at least 75 weight-%, preferably at least 80 weight-%, preferably at least 85 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of reactant(s) and product(s), based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains 25 to 99.9 weight-% of reactant(s) and product(s) based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains at least 25 to 50 weight-%, prefer- ably 26 to 45 weight-%, preferably 30 to 40 weight-% of reactant(s) and product(s) based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains 50 to 99.9 weight-%, preferably 50 to 99.5 weight-%, preferably 60 to 99 weight-%, more preferably 70 to 90 weight-%, more prefer- ably 75 to 80 weight-% of reactant(s) and product(s) based on the total weight of the liquid phase for mono-phase systems or the at least one distinct liquid phase for multi-phase systems.
  • the liquid phase contains 25 to 99.9 weight-% of reactant(s) and product(s) and 0.1 to less than 25 weight-% water.
  • the liquid phase contains at least 50 weight-% of reactant(s) and product(s) and 0.1 to less than 25 weight-% water, preferably 0.1 to 20 weight-% water, preferably 0.1 to 10 weight-% water.
  • the liquid phase contains at least 60 weight-% of reactant(s) and product(s) and 0.1 to less than 25 weight-% water, preferably 0.1 to 20 weight-% water, preferably 0.1 to 10 weight-% water.
  • the liquid phase contains at least 70 weight-% of reactant(s) and product(s) and 0.1 to less than 25 weight-% water, preferably 0.1 to 20 weight-% water, preferably 0.1 to 10 weight-% water. In one embodiment of the invention, the liquid phase contains at least 80 weight-% of reactant(s) and product(s) and 0.1 to less than 25 weight-%, preferably 0.1 to 20 weight-% water, preferably 0.1 to 10 weight-% water.
  • the process according to the invention can be carried out in the presence of a liquid phase which essentially consist of reactant(s), product(s), water and oxidant(s).
  • the process according to the invention can be carried out as a heterogeneous catalyzed process in the presence of a liquid phase which essentially consist of reactant(s), product(s), water and oxidant(s).
  • the process according to the invention can be carried out as a homogenous catalyzed process in the presence of a liquid phase which essentially consist of reactant(s), product(s), water and oxidant(s) and catalyst(s).
  • the liquid phase contains no solvent.
  • solvent encompasses any component other than reactant(s), product(s), water and possibly oxidant(s) or possibly catalyst(s) which is liquid at a temperature of 20 °C and a pressure of 1 bar and which is thus part of the liquid phase.
  • the process can be performed in the presence of a liquid phase, which comprises less than 75 weight-%, preferably less than 70 weight-% solvent based on the total weight of the liquid phase.
  • a suitable solvent can be selected depending on the reactant(s), product(s), catalyst(s), oxidant(s) and reaction conditions.
  • solvent encompasses one or more than one solvents.
  • the following preferred ranges for the solvent content of a liquid phase apply for the liquid phase (for mono-phase systems) or for the at least one distinct liquid phase (for multi-phase systems).
  • the process is performed in a liquid phase, which contains less than 70 weight-%, preferably less than 60 weight-%, preferably less than 50 weight- %, preferably less than 40 weight-%, preferably less than 30 weight-%, more preferably less than 20 weight-%, more preferably less than 10 weight-% solvent based on the total weight of the liquid phase (for mono-phase systems) or the at least one distinct liquid phase (for multi-phase sys- tems).
  • the process according to the invention can be performed in the presence of a liquid phase, which contains less than 5 weight-% solvent based on the total weight of the liquid phase (for mono-phase systems) or the at least one distinct liquid phase (for multi-phase sys- tems).
  • the process is performed in the presence of a liquid phase which contains less than 3 weight-%, preferably less than 1 weight-% of solvent.
  • the process is performed in the presence of a liquid phase which contains no solvent.
  • suitable solvents are for example protic or aprotic solvents.
  • solvents are preferred that have a boiling point above 50°C, for instance in the range of 50 to 200°C, in particular above 65°C, for instance in the range of 65 to 180°C, and specifically above 80°C, for instance in the range of 80 to 160°C.
  • Useful aprotic organic solvents here include, for example, aliphatic hydrocarbons, such as hex- ane, heptane, octane, nonane, decane and also petroleum ether, aromatic hydrocarbons, such as benzene, toluene, the xylenes and mesitylene, aliphatic C3-Cs-ethers, such as 1 ,2-dimethoxy- ethane (DME), diethylene glycol dimethyl ether (diglyme), diethyl ether, dipropyl ether, methyl isobutyl ether, tert-butyl methyl ether and tert-butyl ethyl ether, dimethoxymethane, diethox- ymethane, dimethylene glycol dimethyl ether, dimethylene glycol diethyl ether, trimethylene glycol dimethyl ether, trimethylene glycol diethyl ether, tetramethylene glycol dimethyl
  • those of the aforementioned aprotic sol- vents are preferred that have a boiling point above 50°C, for instance in the range of 50 to 200°C, in particular above 65°C, for instance in the range of 65 to 180°C, and specifically above 80°C, for instance in the range of 80 to 160°C.
  • the solvent is selected from the group consisting of 1 ,2-dimethoxy- ethane (DME), diethylene glycol dimethyl ether (diglyme), diethoxymethane, dimethylene glycol dimethyl ether, tri-methylene glycol dimethyl ether, tetramethylene glycol dimethyl ether, 1 ,3-di- oxolane, 1 ,4-dioxane, 1 ,3,5-trioxane, dimethylacetamide, methyl acetate, dimethyloxalate, meth- oxyacetic acid methyl ester, ethylene carbonate, propylene carbonate, ethylene glycol diacetate and diethylene glycol diacetate, toluene, the xylenes, mesitylene, Cz-Cio-alkanes, such as octane or nonane, THF, 1 ,4-dioxane and mixtures thereof, and specifically selected from toluene
  • DME 1,2-
  • the solvent if employed, is selected from solvents which have a water solubility of greater 150 g/l at 20 °C. In a preferred embodiment the solvent, if employed, is se- lected from solvents which have a vapour pressure of below 100 mbar at 20°C.
  • the process according to the invention can be performed with oxygen and/or hydrogen peroxide as oxidant.
  • Oxygen can be used undiluted or diluted.
  • the oxygen can be diluted with other inert gases like N 2 , Ar or C0 2 , e.g in the form of air.
  • oxygen is used undiluted.
  • Hydrogen peroxide can be used as an aqueous solution, wherein the concen- tration of the aqueous solution will be chosen by a man skilled in the art so as not to exceed the maximum water content of the liquid phase.
  • oxygen is used as oxidant.
  • the process according to the invention can be performed as a heterogeneous catalyzed process or as a homogeneous catalyzed process.
  • the process is conducted as a heterogeneous cata- lysed process.
  • the catalyst and reactant(s)/product(s) are in different phases, which are in contact with each other.
  • the reactant(s)/product(s) are in the liquid phase, whereas the catalyst will be, at least partially in a solid phase.
  • the reaction will take place at the interphase between liquid phase and solid phase.
  • the process according to the invention is carried out in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound (IMC).
  • IMC intermetallic compound
  • An intermetallic compound (IMC) in terms of this invention is a compound made from at least two different metals in an ordered or partially ordered structure with defined stoichiometry.
  • the struc- ture can be similar or different to the structure of the pure constituent metals.
  • Examples for inter- metallic compounds are ordered, partially ordered and eutectic alloys, Laves-phases, Zintl- phases, Heussler-phases, Hume-Rothary-phases, and other intermetallic compounds known to the skilled in the art. Also included are compounds comprising elements belonging to the group of semimetals, like selenides, tellurides, arsenides, antimonides, silizides, germanides and bo- rides.
  • the intermetallic compound comprises at least one catalytically active metal and at least one promotor.
  • At least 50 wt.-%, at least 60 wt.-%, at least 70 wt.-%, prefer- ably the at least 85 wt.-%, preferably at least 90 wt.-% and more preferably at least 95 wt.-% of the at least one catalytically active metal and the at least one promotor are in the structure of an intermetallic compound.
  • the catalytically active metal can be selected from the elements selected from the groups 8, 9, 10 and 1 1 of the periodic table (according to IUPAC nomenclature).
  • the elements of group 8, 9, 10 and 1 1 of the periodic table comprise iron, cobalt, nickel, ruthenium, rhodium, palladium, os- mium, iridium, platinum, copper, silver and gold.
  • the catalytically active metal is selected from elements from the groups 10 and 1 1 of the periodic table (according to IUPAC nomenclature).
  • the catalytically active metal is selected from elements selected from the group consisting of platinum, palladium and gold.
  • the catalytically active metal is platinum.
  • the intermetallic compound preferably comprises at least one promotor, which enhances the activity of the catalytically active metal.
  • promotors are bismuth (Bi), antimony (Sb), lead (Pb), cadmium (Cd), tin (Sn), tellurium (Te), cerium (Ce), selenium (Se) or thallium (Tl).
  • the intermetallic compound comprises at least one promotor selected from the group consisting of bismuth (Bi), antimony (Sb), lead (Pb), cadmium (Cd), tin (Sn) and tellurium (Te).
  • the intermetallic compound comprises at least one promotor selected from the group consisting of bismuth (Bi), lead (Pb) and cadmium (Cd).
  • the catalyst comprises bismuth (Bi).
  • the intermetallic compound comprises as catalytically active metal platinum and as promotor bismuth.
  • Suitable molar ratios of the catalytically active metal and the promotor are in the range from 1 : 0.01 to 1 : 10, preferably 1 : 0.67 to 1 : 5, preferably 1 : 0.5 to 1 : 3, more preferably from 1 : 0.1 to 1 : 2.
  • the catalyst comprises at least one intermetallic compound of the general formula A x B y , wherein
  • A is the at least one catalytically active metal and B is the at least one promotor,
  • x in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • y in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • the catalyst comprises at least one intermetallic compound of the general formula A x B y , wherein
  • A is one or more elements selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag and Au,
  • B is one or more elements selected from Bi, Sb, Pb, Cd, Sn, Te, Ce, Se and Tl
  • x in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • y in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • intermetallic compounds of general formula A x B y wherein
  • A is one or more elements selected from Pd, Pt and Au,
  • B is one or more elements selected from Bi, Pb and Cd,
  • x in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • y in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • A is Pt
  • B is one or more elements selected from Bi, Pb and Cd,
  • x in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • y in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • A is Pt
  • B is Bi
  • x in A x By is in the range 0,05 - 10, preferably from 0,1 to 5, preferably from 0,2 to 4, more prefer- ably 0,25 to 3, more preferably from 0,5 to 2, more preferably from 0,67 to 1.
  • intermetallic compound (IMC) also encompasses mixtures of different intermetallic corn- pounds of general formula A x B y as specified hereinbefore.
  • intermetallic compounds according to this invention are RhPb, RhPb 2 , Rh 4 Pbs,
  • Preferred intermetallic compounds are selected from the group consisting of PtBi, PtBi 2 , Pt 2 Bi3 , PtPb, PtsPb, PtPb 2 , PtPb 4 , PtSb, PtSb 2 , Pto.3Sbo.7, PtsSb, Pt3Sb 2 , Pt7Sb, PtSn, Pto.gSno.i, Pto.94Sno.06, PtSn 2 , PtSn 4 , Pt 2 Sn 3 , and Pt 3 Sn
  • Preferred intermetallic compounds are selected from the group consisting of PtBi, PtBi 2 and Pt 2 Bi3.
  • intermetallic compounds can be detected by standard methods for charac- terizing solids, like for example electron microscopy, solid state NMR, XPS (X-ray photoelectron spectroscopy) or Powder X-Ray Diffraction (PXRD).
  • PXRD-analysis can preferably be employed for unsupported intermetallic compounds, whereas XPS analysis is preferred for the analysis of supported intermetallic compounds.
  • PXRD-analysis can for example be performed as described in Zhang et al., J. Am. Chem. Soc. (2015) 137, p 6264“Characterization of Pt-Bi intermetallic NPs” or as described in Cui et al., J Am. Chem. Soc. (2014), 136, 10206-10209 and the Support- ing Information thereto.
  • XPS can for example be performed as described in the examples below.
  • IMCs intermetallic compounds
  • IMCs can be prepared by standard methods, for example as described in Zhang et al., J. Am. Chem. Soc. (2015) 137, 6263-6269; Zhang et. al., Electrochemistry Communications (2012) 25, 105-108 or Furukawa et al., RSC Adv. (2013), 3, 23269-23277. IMCs can also be prepared by the so called“DiSalvo” Method, as described in Cui et al., J. Am. Chem. Soc. (2014), 136, 10206- 10209 or Chen et al. (2012), J. Am. Chem. Soc. 134, 18453-18459. IMCs can also for example be prepared as described in WO 2018073367.
  • intermetallic compounds are obtainable by g-1 ) providing a composition comprising the at least one metal compound and the at least one promotor compound
  • IMCs are obtainable in a reaction, which combines steps g-1 ) and g-2) or steps g-2) and g-3).
  • the metal compound and the promotor compound can be provided for example as described in step-b) herein.
  • the metal compound and the promotor compound are provided in a solvent, preferably in an aprotic solvent as describe above.
  • the metal compound and the promotor compound are pro- vided as chlorides.
  • the reducing of the composition is preferably performed as described in step e) herein for the reduction of the catalyst precursor.
  • step g-2 In case the reducing agent in step g-2) is provided in a solvent, it is preferred that the solvent is identical to the solvent of composition provided in step g-1 ).
  • the reducing agent is selected from the group consisting of potassium triethyl borohydride (K(C H 5 ) BH) and lithium triethyl borohydride (Li(C H 5 ) BH).
  • step g-1 ) and step g-2) are performed in a one pot reaction.
  • step g-1 ) and step g-2) are performed in a one pot reaction
  • the metal compound and the promotor compound are provided as chlorides and the reducing agent is selected from potassium triethyl borohydride (K((C H 5 ) BH) and lithium triethyl borohy- dride (Li(C H 5 ) BH).
  • the generated insoluble by-product KCI or LiCI then serves as a matrix that stabilizes the IMCs generated and minimizes agglomeration.
  • such a one pot reaction is performed in an aprotic solvent, for example in THF.
  • a stabilizer preferably an inor- ganic stabilizer can be added to the composition in step g-2) or a reducing agent, which also serves as stabilizer can be employed.
  • a solvent which also serves as a stabilizer can be employed in step g-4 (for example ethylene glycol).
  • the annealing step is preferably performed by treatment of the composition obtained in step g- 2) at temperatures between 200 to 700 °C.
  • steps g-2) and g-3) can be combined into a single step by thermal treatment of the composition obtained in step g-1 ) in the presence of a reducing agent or at a temperature where reduction occurs.
  • the IMCs can be employed directly as obtained after the annealing step.
  • the IMCs can be recovered, for example by suitable separation means such as filtration and/or centrifugation.
  • the recovery step can preferably be performed in the presence of a stabilizer, such as for example PVP or ethylene glycol.
  • the so obtainable IMCs can be of various sizes, for example in the range of 1 to 50 nm, prefer- ably 5 to 30 nm, but can also be in the size of pm (agglomerates).
  • the size of the IMC can be adjusted by means known to a person skilled in the art, for example by choice of solvent and/or stabilizer and/or time of the annealing step.
  • the structure of the IMCs is generally adjusted by varying the temperature of the annealing step.
  • the intermetallic compound can be used in any form, e.g. unsupported or on a support.
  • the intermetallic compound can be used in an unsupported form, for example as a powder, a mesh, a sponge, a foam or a net.
  • the intermetallic compound is on a support.
  • the term“on a support” encompasses that the intermetallic compound can be located on the outer surface of a support and/or on the inner surface of a support. In most cases, the intermetallic compound will be located on the outer surface of a support and on the inner surface of a support.
  • the catalyst comprises the catalytically active metal(s), the promotor(s) and the support.
  • the support can for example be a powder, a shaped body or a mesh, for example a mesh of iron-chromium-aluminium (FeCrAI), that was tempered in the presence of oxygen (commercially available under the trademark Kanthal ® ).
  • FeCrAI iron-chromium-aluminium
  • the intermetallic compound is on a support.
  • the intermetallic compound is on a support and the support is selected from the group consisting of powders and shaped bodies.
  • powders usually have a particle size in the range of 1 to 200 pm, preferably 1 to 100 pm.
  • the shaped bodies can for example be obtained by extrusion, pressing or tableting and can be of any shape such as for example strands, hollow strands, cylinders, tablets, rings, spherical particles, trilobes, stars or spheres. Typical dimensions of shaped bodies range from 0.5 mm to 250 mm.
  • the support has a diameter from 0.5 to 20 mm, preferably from 0.5 to 10 mm, more preferably from 0.7 to 5 mm, more preferably from 1 to 2.5 mm, preferably 1 .5 to 2.0 mm.
  • the support is obtained by extrusion and is in the form of a strand or hollow strand.
  • a support is employed with strand diameters from 1 to 10 mm, preferably 1.5 to 5 mm.
  • a support is employed with strand lengths from 2 to 250 mm, preferably 2 to 100 mm, preferably 2 to 25 mm, more preferably 5 to 10 mm.
  • a support is employed with a strand diameter of 1 to 2 mm and strand lengths of 2 to 10 mm.
  • the intermetallic compound is on a support, wherein the support is selected from the group consisting of carbonaceous and oxidic materials.
  • Suitable support materials are for example carbonaceous or oxidic materials.
  • a preferred carbonaceous support is activated carbon.
  • the surface area of carbonaceous support materials preferably is at least 200 m 2 /g, preferably at least 300 m 2 /g. In case a carbonaceous support is used an activated carbon with a surface area of at least 300 m 2 /g is preferred.
  • the intermetallic compound is on an activated carbon support, preferably with an activated carbon support with a surface area of at least 300 m 2 /g.
  • the oxides of the following elements can be used: Al, Si, Ce, Zr, Ti, V, Cr, Zn, Mg.
  • the invention also encompasses the use of mixed oxides comprising two or more elements.
  • mixed oxides are used as support se- lected from the group consisting of (Al/Si), (Mg/Si) and (Zn/Si) mixed oxides.
  • an oxidic support is used, selected from the group consisting of aluminum oxide and silcium dioxide.
  • Aluminium oxide can be employed in any phase, such as alpha aluminium oxide (0AI2O3), beta aluminium oxide (b-A ⁇ 2q3), gamma aluminium oxide (Y-AI2O3,), delta aluminium oxide (b-AhCh), eta aluminium oxide (g-A Os), theta aluminium oxide (Q-AI2O3), chi aluminium oxide (X-AI2O3), kappa aluminium oxide (K-AI2O3) and mixtures thereof.
  • beta aluminium oxide (b-AI 2 0 3 ) describes the compound Na20 HAI2O3.
  • the oxidic support is selected from the group consisting of alpha alu- minium oxide (0AI2O3), beta aluminium oxide (b-A ⁇ 2q3), gamma aluminium oxide (Y-AI2O3), delta aluminium oxide (b-AbC ), and theta aluminium oxide (Q-AI2O3).
  • the oxidic support is selected from the group consisting of alpha alu- minium oxide (0AI2O3), beta aluminium oxide (b-A ⁇ 2q3) and gamma aluminium oxide (Y-AI2O3).
  • the oxidic support is gamma aluminium oxide (Y-AI2O3).
  • Y-AI2O3 gamma aluminium oxide
  • the oxidic supports can have a BET-surface area (BET, Brunnauer-Emmet- Teller determined according to DIN 66131 by N2 adsorption at 77 K) from 0.1 to 500 m 2 /g.
  • BET Brunnauer-Emmet- Teller
  • the oxidic supports have a BET-surface area of at least 0.1 m 2 /g, preferably at least 1 m 2 /g, preferably at least 10 m 2 /g, more preferably of at least 30 m 2 /g, more preferably of at least 50 m 2 /g, more preferably of at least 75 m 2 /g, preferably of at least 100 m 2 /g, preferably of at least 150 m 2 /g especially preferred of at least 200 m 2 /g.
  • the oxidic support has a BET-surface area of 1 m 2 /g to 50 m 2 /g. In a further embodiment, the oxidic support has a BET-surface area of 10 m 2 /g to 300 m 2 /g, preferably of 20 to 100 m 2 /g. In a further embodiment, the oxidic support has a BET-surface area of 100 m 2 /g to 300 m 2 /g, preferably 150 to 300 m 2 /g.
  • the support is AI2O3 with a BET-surface area of 100 to 300 m 2 /g.
  • the intermetallic compound comprises platinum and bismuth and is on a support.
  • the intermetallic compound comprises platinum and bismuth and is on a support, wherein the support is selected from carbonaceous and oxidic materials.
  • the intermetallic compound comprises platinum and bismuth and is on a support, wherein the support is selected from carbonaceous and oxidic materials, and wherein the oxidic material is selected from the group consisting of oxides of the elements selected from the group consisting of Al, Ce, Zr, Ti, V, Cr, Zn and Mg.
  • the intermetallic compound comprises platinum and bismuth and is on a support, wherein the support is selected from carbonaceous materials and oxidic materials, and wherein the oxide is selected from the group consisting of oxides of the elements selected from the group consisting of Al, Ce, Zr and Ti.
  • the intermetallic compound on a support is selected from the group consisting of platinum-bismuth intermetallic compounds on carbon and platinum-bismuth inter- metallic compounds on aluminium oxide.
  • the intermetallic compound on a support is selected from the group consisting of PtBi/C, PtBh/C, Pt2Bi3/C, PtBi/AhCh, PtBh/AhCh, and Pt2Bi3/Al2C>3.
  • the intermetallic compound comprises platinum and bismuth and is on an aluminium oxide support, wherein the aluminium oxide is selected from the group consisting of alpha aluminium oxide (0AI2O3), beta aluminium oxide (b-A ⁇ 2q3), gamma aluminium oxide (g- AI2O3,), delta aluminium oxide (b-A C ), eta aluminium oxide (g-A Os), theta aluminium oxide (Q- AI2O3), chi aluminium oxide (X-AI2O3) and kappa aluminium oxide (K-AI2O3).
  • the aluminium oxide is selected from the group consisting of alpha aluminium oxide (0AI2O3), beta aluminium oxide (b-A ⁇ 2q3), gamma aluminium oxide (g- AI2O3,), delta aluminium oxide (b-A C ), eta aluminium oxide (g-A Os), theta aluminium oxide (Q- AI2O3), chi aluminium oxide (X-AI2O3) and kappa aluminium oxide (K
  • the content of the catalytically active metal of the catalyst usually is in the range of 0.1 to 20 weight-%, preferably 0.1 to 15 weight-%, pref- erably in the range of 0.5 to 10 weight-%.
  • the catalyst can for example be prepared by
  • the catalyst is obtainable by, preferably obtained by
  • the catalyst is obtainable by, preferably obtained by
  • composition comprising the at least one metal compound and the at least one promotor compound
  • the catalyst is obtainable by, preferably obtained by a) providing a support
  • composition comprising the at least one metal compound and the at least one promotor compound
  • Step a) Providing a support
  • a suitable support is provided, for example by adding the support in form of a powder or a shaped body directly to a reactor vessel or by providing the support as a slurry (in case the support is in form of a powder).
  • Step b) Providing a composition comprising the at least one metal compound and the at least one promotor compound
  • the metal compound is a precursor of the catalytically active metal.
  • the catalytically active metal is obtained by reduction of the metal compound.
  • the promotor compound is a precursor of the promotor.
  • the promotor is obtained conversion (by oxidation and/or reduction) of the promotor compound to the promotor.
  • the metal compound and the promotor compound can be employed as solution, for example as an aqueous solution of a water-soluble salt of the at least one metal compound and the at least one promotor or as a non-aqueous solution. They can also be employed as a colloid in which the non-dissolved metal compound and/or promotor compound are dispersed in a liquid phase.
  • the metal compound is employed as a salt.
  • aqueous or non-aqueous solutions can be employed.
  • Suitable salts of the metal compound include nitrates, acetates, sulphates, citrates, oxides, hy- droxides and chlorides and combinations thereof.
  • Preferably water-soluble salts are used.
  • the metal compound is selected from the group consisting of platinum salts.
  • aqueous or non-aqueous solutions of the platinum salt can be employed.
  • the platinum salt is selected from the group consisting of H 2 PtCl 6 , Pt(NH 3 ) 2 (N0 3 ) 2 , Pt(N0 2 ) 2 (NH 3 ) 2 /NH 4 0H and Pt(N0 3 ) 2 .
  • Suitable salts of the promotor compound include nitrates, acetates, sulphates, citrates, oxides, hydroxides and chlorides and combinations thereof.
  • Preferably water-soluble salts are used.
  • the promotor compound is selected from the group consisting of Bi salts, Cd salts and Pb salts.
  • the metal compound and the promotor compound can be provided as separate compositions and deposited separately on the support.
  • the deposition is performed by immersion and/or spraying.
  • the composition obtained in step b) can be employed as solution or as colloid or as a colloid which is generated in situ during the immersion or spraying.
  • the deposition by immersion or spraying can be performed at a temper- ature of 1 to 100 °C.
  • the pH value at which the deposition step is performed can be chosen depending on the metal compound and or promotor compound used.
  • the deposition can be per- formed from 0.1 to 24 hours, usually from 0.5 to 2 hours.
  • the deposition can be performed at different pressures, for example at pressures from 1 to 1000 mbar (atmospheric pressure), suita- ble pressures are for example 50 mbar, 70 mbar, 100 mbar, 250 mbar, 500 mbar or atmospheric pressure.
  • the so obtained catalyst precursor can optionally be dried and/or calcined prior to the reduction step.
  • the volume of the solution or colloid of the composition obtained in step b) is ideally chosen, so that at least 90%, preferably 100% of the pore volume of the support will be filled with the solution or colloid (so called“incipi- ent-wetness” method).
  • the concentration of the metal compound in the composition obtained in step b) is ideally chosen so that, after deposition and reduction, a catalyst with the desired content of catalytically active metal is obtained.
  • the deposition step can be conducted in one step or in multiple, consecutive steps.
  • the deposi- tion step can also be performed as a combination of spraying and immersion.
  • the catalyst precursor can then be recovered by suitable separation means such as filtration and/or centrifugation.
  • the catalyst precursor can then be washed with water, preferably until a conductivity of less than 400 pS/cm, preferably less than 200 pS/cm is obtained.
  • a drying step and/or a calcination step d) can be performed subsequent to the deposition step c).
  • the calcination step d) can be performed in customary furnaces, for example in rotary furnaces, in chamber furnaces, in tunnel furnaces or in belt calciners.
  • the calcination step d) can be performed at temperatures from above 200°C to 1 150°C, prefera- bly from 250 to 900°C, preferably from 280°C to 800°C and more preferably from 500 to 800 °C, preferably from 300°C to 700°C.
  • the calcination is suitably conducted for 0.5 to 20 hours, prefer- ably from 0.5 to 10 hours, preferably from 0.5 to 5 hours.
  • the calcination of the catalyst precursor in step d) mainly serves the purpose to stabilize the metal compound and the promotor compound deposited on the support and to remove undesired com- ponents.
  • the so obtained catalyst precursor can then be reduced, for example by treatment with a gas (gas phase reduction) or by treatment of the catalyst precursor with a solution of a reducing agent (liquid phase reduction).
  • the gas phase reduction of the catalyst precursor can be performed by treating the catalyst precursor with hydrogen and/or CO.
  • the hydrogen and/or CO can further comprise at least one inert gas, such as for example helium, neon or argon, N 2 , C0 2 and/or lower alkanes, such as methane, ethane, propane and/or butane.
  • N 2 is employed as the inert gas.
  • the gas phase reduction can be performed at temperatures from 30°C to 200 °C, preferably from 50°C to 180°C, more preferably from 60 to 130°C. Usually the gas phase reduction is performed over a period from 1 to 24 hours, preferably 3 to 20 hours, more preferably 6 to 14 hours.
  • the liquid phase reduction of the catalyst precursor is performed by treating the catalyst pre- cursor with a solution of a reducing agent.
  • Suitable reducing agents are quaternary alkyl ammo- nium salts; formic acid; salts of formic acid, such as sodium formate, potassium formate, lithium formate or ammonium formate; citric acid; salts of citric acid such as sodium citrate, potassium citrate, lithium citrate, ammonium citrate; ascorbic acid; salts of ascorbic acid such as sodium ascorbate, potassium ascorbate, lithium ascorbate and ammonium ascorbate; tartaric acid; salts of tartaric acid, such as sodium tartrate, potassium tartrate, lithium tartrate and ammonium tar- trate; oxalic acid; salt of oxalic acid, such as potassium oxalate, sodium oxalate, lithium oxalate and ammonium oxalate; ammonium hydrogen carbonate (NH4HCO3); hydroxy
  • the liquid phase reduction can be performed at a temperature from 10 to 95°C, preferably from 50 to 90°C.
  • the pH of the reduction step can be chosen depending on the reducing agent used.
  • the reduction step is performed by treatment of the catalyst precursor with a solution of a reducing agent.
  • the reduction step is performed by treatment of the catalyst precursor with a solution of a reducing agent, wherein the reducing agent is selected from the group con- sisting of quaternary alkyl ammonium salts; formic acid; salts of formic acid, such as sodium formate, potassium formate, lithium formate or ammonium formate; citric acid; salts of citric acid such as sodium citrate, potassium citrate, lithium citrate, ammonium citrate; ascorbic acid; salts of ascorbic acid such as sodium ascorbate, potassium ascorbate, lithium ascorbate and ammo- nium ascorbate; tartaric acid; salts of tartaric acid, such as sodium tartrate, potassium tartrate, lithium tartrate and ammonium tartrate; oxalic acid; salt of oxalic acid, such as potassium oxalate, sodium oxalate, lithium oxalate and ammonium oxalate; ammonium hydrogen carbonate (NH 4 HC0
  • the reduction step is performed by treatment of the catalyst precursor with a solution of a reducing agent, wherein the reducing agent is selected from the group con- sisting of sodium formate, sodium citrate, sodium ascorbate, polyols, reducing sugars, formalde- hyde, methanol, ethanol, 2-propanol, potassium triethyl borohydride (K(C H 5 ) BH) and lithium tri- ethyl borohydride (Li(C H 5 ) BH).
  • the reducing agent is selected from the group con- sisting of sodium formate, sodium citrate, sodium ascorbate, polyols, reducing sugars, formalde- hyde, methanol, ethanol, 2-propanol, potassium triethyl borohydride (K(C H 5 ) BH) and lithium tri- ethyl borohydride (Li(C H 5 ) BH).
  • the catalyst can then be recovered by suitable separation means such as filtration and/or centrif- ugation. Typically, the catalyst is then washed with water, preferably until a conductivity of less than 400 pS/cm, preferably less than 200 pS/cm is obtained.
  • Drying steps can be performed for example subsequent to step c) and/or subsequent to step e).
  • the drying of the catalyst precursor obtained in step c) or of the catalyst obtained in step e) can generally be performed at temperatures above 60°C, preferably above 80°C, more preferably above 100°C.
  • the drying can for example be performed at temperatures from 120 °C up to 200 °C.
  • the drying will normally be performed until substantially all the water is evaporated. Common drying times range from one to up to 30 hours and depend on the drying temperature.
  • the drying step can be accelerated by the use of vacuum.
  • the annealing step is preferably performed by treatment of the catalyst obtained in step e) at temperatures between 200 to 700 °C.
  • steps e) and f) can be combined into a single step by thermal treat- ment of the precursor obtained in step c) in the presence of a reducing agent or at a tempera- ture where reduction occurs.
  • the annealing step is preferably performed at temperatures between 200 to 700 °C, preferably under chemically inert conditions.
  • the annealing step is the step in which the IMC structure is mainly generated.
  • the extend of the IMC structure can be adjusted for example by varying the temperature or the duration of the an- nealing step.
  • the extent to which the IMCs structure is obtained can be monitored for example by PXRD analysis. If needed, the temperature and/or time of thermal treatment can be adapted, to achieve the desired extend of IMC structure.
  • the annealing steps g-3) or f) are performed by heating the composition obtained in step g-2) or the catalyst obtained in step c) to the desired temperature under chemically inert conditions wherein the gas mixture present does not contain any reactive components that can undergo chemical reaction with the composite material.
  • the mixture should not corn- prise oxidizing agents like for example oxygen, water, NO x , halides or there like.
  • the heating can be performed by any method suited to heat solids or wet solids like heating in muffle fur- naces, microwaves, rotary kilns, tube furnaces, fluidized bed and other heating devices known to the person skilled in the art.
  • the intermetallic compound in case the intermetallic compound is on a support, it can be evenly distributed on the support or can be unevenly distributed on the support. It can for example be concentrated in the core or in defined layers of the support.
  • the intermetallic compound can be located partially or completely on the inner surface of the support or can be located partially or completely on the outer surface of the support. In case the intermetallic compound is located completely on the inner surface of the support, the outer surface of the catalyst is identical to the outer surface of the support.
  • the distribution of the intermetallic compound, the catalytically active metal and the promotor can be determined with Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray Spec- troscopy (EDXS).
  • the distribution can for example be determined by preparing a cross section of the catalyst. In case the catalyst is a sphere the cross section can be prepared through the center of the sphere. In case the catalyst is a strand, the cross section can be prepared by cutting the strand at a right angle to the axis of the strand. Via backscattered electrons (BSE) the distribution of the catalytically active metal in the catalyst can be visualized.
  • BSE backscattered electrons
  • the amount of intermetallic corn- pound, the catalytically active metal and the promotor can then be quantified via EDXS whereby an acceleration voltage of 20 kV is usually used.
  • a catalyst is employed, wherein the intermetallic corn- pound is located in the outer shell of the catalyst.
  • the intermetallic compound is mainly located in the outer shell of the catalyst.
  • the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • X is 15% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • the outer shell is the space from the outer surface to a depth of 1 12.5 pm from the outer surface.
  • the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • X is 30% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • the outer shell is the space from the outer surface to a depth of 225 pm from the outer surface.
  • the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 100 pm from the outer surface of the catalyst. In one embodiment, the outer shell is the space from the outer surface of the catalyst to a depth of 400 pm, preferably 300 pm, preferably 200 pm from the outer surface of the catalyst.
  • At least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the inter- metallic compound is located in the outer shell of the catalyst, wherein the outer shell of the cat- alyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • At least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • At least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 100 pm from the outer surface of the catalyst.
  • At least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 400 pm, preferably to a depth of 300 pm, preferably to a depth of 200 pm from the outer surface of the catalyst.
  • a catalyst is employed, wherein the dispersity of the intermetallic compound is on average in the range of 10% to 100%, preferably 30% to 95% (de- termined with CO-sorption according to DIN 66136-3).
  • Catalysts in which the intermetallic compound is located in the outer shell of the catalyst can for example be obtained by the deposition-reduction method as described above.
  • the distribution of the intermetallic compound in the outer shell of the catalyst can be effected for example by the choice of the deposition method and/or the choice of the deposition parameters such as temper- ature, pH and time and the combination of these parameters.
  • a description of the different meth- ods of preparation can for example be found in ..Handbook of Heterogeneous Catalysis", edited by G. Ertl, H. Knozinger, J. Weitkamp, Vol 1 . Wiley-VCH, 1997. Chapter 2, part 2.2.1 .1. Impreg- nation and Ion Exchange, authors M. Che, O. Clause, and Ch. Marcilly, p. 315-340.
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar,
  • a catalyst which is obtainable by, preferably obtained by a) providing a support
  • composition comprising the at least one metal compound and the at least one promotor compound
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 - alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R 1 , R 2 and R 3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar,
  • a catalyst which is obtainable by, preferably obtained by o providing a support,
  • the intermetallic compound comprises platinum as catalytically active metal.
  • the intermetallic corn- pound comprises bismuth as promotor.
  • the support is selected from the group consisting of of alpha aluminium oxide (0AI 2 O 3 ), beta aluminium oxide (b-AI 2 0 3 ) and gamma aluminium oxide (Y-AI 2 O 3 ).
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 - alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R 1 , R 2 and R 3 have the meaning as given above
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar, wherein a catalyst is used, which comprises the at least one intermetallic corn- pound on a support and wherein the at least one intermetallic compound is mainly located in the outer shell of the catalyst.
  • a catalyst which comprises the at least one intermetallic corn- pound on a support and wherein the at least one intermetallic compound is mainly located in the outer shell of the catalyst.
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar,
  • a catalyst which comprises the at least one intermetallic corn- pound on a support and wherein at least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, prefer- ably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar,
  • a catalyst which comprises the at least one intermetallic corn- pound on a support and wherein at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound, all weight-% based on the total weight of the liquid phase, determined at a temperature of 20 °C and a pressure of 1 bar,
  • a catalyst which comprises the at least one intermetallic corn- pound on a support and wherein at least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, prefer- ably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 1 00 pm from the outer surface of the catalyst.
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst and in the presence of a liquid phase
  • liquid phase contains 0.1 to less than 25 weight-% water
  • liquid phase contains at least 25 weight-% of alcohol(s) of general formula (II) and alpha, beta unsaturated aldehyde(s) of general formula (I) and
  • oxidant is oxygen and/or hydrogen peroxide
  • the catalyst comprises at least one intermetallic compound
  • a catalyst which comprises the at least one intermetallic compound on a support and wherein at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 400 pm, prefer- ably to a depth of 300 pm, preferably to a depth of 200 pm from the outer surface of the catalyst.
  • the intermetallic compound comprises platinum as catalytically active metal.
  • the intermetallic corn- pound comprises bismuth as promotor.
  • the support is selected from the group consisting of of alpha aluminium oxide (0AI 2 O 3 ), beta aluminium oxide (b-AI 2 0 3 ) and gamma aluminium oxide (Y-AI 2 O 3 ).
  • a catalyst comprising the at least one intermetallic compound on a support can advantageously be used for the preparation of alpha, beta unsaturated alde- hydes of formula (I).
  • SA specific activities
  • Suitable catalysts comprising the at least one intermetallic compound on a support are the ones describe above with all preferred embodiments.
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 - alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R 1 , R 2 and R 3 have the meaning as given above in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound,
  • composition comprising the at least one metal compound and the at least one promotor compound
  • One embodiment of the invention is directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • the catalyst comprises at least one intermetallic compound
  • IMC intermetallic compound
  • the oxidation is performed at a temperature from 1 to 250 °C; preferably from 5 to 150 °C, more preferably from 20 to 100 °C.
  • the intermetallic compound comprises platinum as catalytically ac- tive metal.
  • the intermetallic compound comprises bismuth as promotor.
  • the support is selected from the group consisting of of alpha aluminium oxide (0AI 2 O 3 ), beta aluminium oxide (b-A ⁇ 2 q 3 ) and gamma aluminium oxide (Y-AI 2 O 3 ).
  • the oxidant is oxygen and/or hydrogen peroxide.
  • Suitable catalysts comprising the at least one intermetallic compound on a support are the ones describe above with all preferred embodiments.
  • a further aspect of the invention is directed to the process for the preparation of alpha, beta un- saturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • R1, R 2 and R3 have the meaning as given above in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound,
  • a further aspect of the invention is therefore directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R3, independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C2-C6-alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from NO2, CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • Ri, R 2 and R3 have the meaning as given above in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound,
  • the at least one intermetallic compound is on a support and wherein at least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic corn- pound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 15% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • a further aspect of the invention is therefore directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • Ri, R 2 and R3 have the meaning as given above in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound,
  • the at least one intermetallic compound is on a support and wherein at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of X from the outer surface of the catalyst, wherein X is 30% of the distance from the outer surface of the catalyst to the center of the catalyst.
  • a further aspect of the invention is therefore directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • R 1 , R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C1-C6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C1-C6 alkoxy, (C1-C6- alkoxy)carbonyl, C1-C6 acyl, C1-C6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • Ri, R 2 and R 3 have the meaning as given above in the presence of a catalyst, wherein the catalyst comprises at least one intermetallic compound,
  • the at least one intermetallic compound is on a support and wherein at least 50 weight-%, preferably at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic corn- pound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 100 pm from the outer surface of the catalyst.
  • a further aspect of the invention is therefore directed to the process for the preparation of alpha, beta unsaturated aldehydes of general formula (I)
  • Ri, R 2 and R 3 independently of one another, are selected from hydrogen; Ci-C 6 -alkyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C 1 -C 6 alkoxy, (Ci-C 6 -alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; and C 2 -C 6 -alkenyl, which optionally carry 1 , 2, 3, or 4 identical or different substituents which are selected from N0 2 , CN, halogen, C 1 -C 6 alkoxy, (C 1 -C 6 - alkoxy)carbonyl, C 1 -C 6 acyl, C 1 -C 6 acyloxy and aryl; by oxidation of alcohols of general formula (II)
  • Ri, R 2 and R 3 have the meaning as given above in the presence of a catalyst
  • the catalyst comprises at least one intermetallic compound, wherein the at least one intermetallic compound is on a support and wherein at least 70 weight-%, preferably at least 80 weight-%, preferably at least 90 weight-%, preferably at least 95 weight-% of the at least one intermetallic compound is located in the outer shell of the catalyst, wherein the outer shell of the catalyst is the space from the outer surface of the catalyst to a depth of 400 pm, preferably to a depth of 300 pm, preferably to a depth of 200 pm from the outer surface of the catalyst.
  • the oxidation is performed at a temperature from 1 to 250 °C; preferably from 5 to 150 °C, more preferably from 20 to 100 °C.
  • the intermetallic compound comprises platinum as catalytically ac- tive metal.
  • the intermetallic compound comprises bismuth as promotor.
  • the support is selected from the group consisting of of alpha aluminium oxide (0AI 2 O 3 ), beta aluminium oxide (b-A ⁇ Ob) and gamma aluminium oxide (Y-AI 2 O 3 ).
  • the oxidant is oxygen and/or hydrogen peroxide.
  • the process is conducted as a batch process and the molar ratio of the catalytically active metal to the alcohol(s) of general formula (II) is in the range 0.0001 : 1 to 1 : 1 , more preferably in the range 0.001 : 1 to 0.1 : 1 and even more preferably in the range 0.001 : 1 to 0.01 : 1.
  • the process is conducted as a continuous process and the catalyst load (defined as total amount of alcohol of general formula (II)/ total amount of catalytically active metal in the reactor/time unit) is in the range 0.01 to 100 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour, more preferably in the range 0.1 to 20 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour.
  • the catalyst load (defined as total amount of alcohol of general formula (II)/ total amount of catalytically active metal in the reactor/time unit) is in the range 0.01 to 100 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour, more preferably in the range 0.1 to 20 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour.
  • the process is conducted as a continuous process and the catalyst load (defined as total amount of alcohol of general formula (II)/ total amount of catalytically active metal in the reactor/time unit) is in the range 30 to 40000 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour, more preferably in the range 1000 to 9000, more preferably in the range 1200 to 5000, preferably 1500 to 4000, preferably in the range of 1650 to 3500 g of alcohol(s) of general formula (II) per g of catalytically active metal per hour.
  • the process according to the invention can be performed in reaction vessels customary for such reactions, the reaction being configurable in a continuous, semi-batch or batch-wise mode. In general, the particular reactions will be performed under atmospheric pressure. The process may, however, also be performed under reduced or increased pressure.
  • the process according to the invention can be performed under pressure, preferably under a pressure between above 1 bar and 15 bar (absolute), preferably between above 1 bar and 10 bar (absolute).
  • the process according to the invention can be performed at a partial pressure of oxygen from 0.1 to 15 bar, preferably from 0.2 to 10 bar, preferably from 0.2 to 8 bar, more preferably from 0.2 to 5 bar, more preferably from 1 to 3, preferably from 1 to 2.5, more preferably from 1.2 to 2 bar.
  • the process is conducted as a batch process. In a preferred embodiment of the invention the process is conducted as a semi-batch process. In a preferred embodiment of the invention the process is conducted as a continuous process.
  • the process is conducted with a fixed-bed catalyst.
  • suitable fixed- bed reactors can be selected from the group consisting of trickle-bed reactors, bubble-packed reactors, multi-tubular reactors and plate reactors.
  • the process according to the invention can be conducted in one fixed-bed reactor or can prefer- ably be conducted in more than one, preferably more than two, more preferably more than three, preferably three to five fixed-bed reactors.
  • the one or more fixed-bed reactors can be arranged in series or in parallel.
  • the process according to the invention can be conducted at common values of weight hourly space velocity (WHSV), defined as the hourly mass flow of the process feed (in kg/h) per catalyst (in kg).
  • WHSV weight hourly space velocity
  • the process can for example be performed at WHSV values of 1 to 20000, preferably 10 to 10000, preferably 20 to 5000, preferably 20 to 500, more preferably from 50 to 100 kg/kg/h.
  • the process according to the invention can be conducted in one or more fixed-bed reactor(s) with or without heat exchange.
  • the fixed-bed reactor(s) can be operated so that a constant temperature is held over one, some or all fixed-bed reactors.
  • the fixed-bed reactor(s) can be operated so that a defined temper- ature gradient is maintained over one, some or all fixed-bed reactors without heat addition or removal.
  • the fixed-bed reactor(s) can be operated with a temperature-controlled profile, wherein a defined temperature profile is maintained over one, some or all fixed-bed reactors with internal or external heat addition or removal.
  • the process is conducted in a trickle-bed reactor with a fixed-bed catalyst.
  • the process is conducted with more than one, preferably more than two, more preferably more than three trickle-bed reactors, which are arranged in series or in parallel, preferably in series.
  • the process is conducted with three to five trickle-bed reactors, which are arranged in series.
  • one or more, preferably each of the trickle-bed reactors can be provided with a liquid recycle stream.
  • the components of the reaction can be in- serted to the reactor concurrently, meaning that the liquid phase(s) and the gas phase comprising the oxidant oxygen, are inserted to the reactor at the same side, preferably at the top of the reactor.
  • the process is conducted in a bubble-packed reactor with a fixed-bed catalyst. In one embodiment of the invention, the process is conducted with more than one, preferably more than two, more preferably more than three bubble-packed reactors, which are arranged in series or in parallel, preferably in series. In one embodiment, the process is conducted with three to five bubble-packed reactors, which are arranged in series.
  • the components of the reaction can be inserted in the reactor concurrently, meaning that the liquid phase(s) and the gas phase comprising the oxidant oxygen, are inserted to the reactor at the same side, preferably at the bottom of the reac- tor.
  • the components of the reaction can be inserted in the reactor countercurrently, meaning that the liquid phase(s) and the gas phase corn- prising the oxidant oxygen, are inserted to the reactor at opposite sides.
  • the liquid phase(s) are inserted to the reactor at the bottom of the reactor, whereas the gas phase comprising oxygen as oxidant is inserted at the top of the reactor.
  • the liquid phase(s) are inserted to the reactor at the top of the reactor, whereas the gas phase comprising oxygen as oxidant is inserted at the bottom of the reactor.
  • the process is conducted as a slurry process.
  • the process can be conducted in a slurry-based system as stirred tank reactor or slurry bubble col- umn.
  • reaction is carried out by contacting alcohol(s) of general formula (II), water, catalyst, the oxidant and optional components, such as for example one or more solvent(s), under suitable reaction conditions.
  • these components can in principle be contacted with one another in any desired sequence.
  • the alcohol(s) of general formula (II) if appropriate dissolved in water or a solvent or in dispersed form, can be initially charged and admixed with the catalyst or, conversely, the catalytic system can be initially charged and admixed with the alcohol(s) of general formula (II) and water.
  • these components can also be added simultaneously to the reaction vessel.
  • a stirred tank reactor can be used where the cat- alyst, the reactant, water, hydrogen peroxide (if used as oxidant) and optionally solvent are loaded. In case oxygen is used as oxidant, the reactor is then pressurized with oxygen. The re- action is then performed until the desired conversion is achieved.
  • a stirred tank reactor can be used where the cat- alyst, the reactant(s), if appropriate dissolved in water or solvent or in dispersed form, water, hydrogen peroxide (if used as oxidant) and optionally one or more solvent(s) are loaded.
  • the reactor is then pressurized with oxygen. The reaction is then per- formed until the desired conversion is achieved.
  • a stirred tank reactor can be used where the catalyst, the reactant(s), water, hydrogen peroxide (if used as oxidant) and optionally solvent are loaded. In case oxygen is used as an oxidant, the oxygen is then continuously fed to the reactor until the desired conversion is achieved.
  • a fixed bed catalyst in a trickle-bed reactor can be used. The solution of reactant(s), water, hydrogen peroxide (if used as oxidant), optionally comprising solvent, are then pumped in a loop over the catalyst.
  • oxygen is passed as a continuous stream through the reactor.
  • the oxygen can be added in excess, the excess being released to the off gas, alternatively the oxygen can be added in an amount required to replenish the con- sumed oxygen.
  • a continuous stirred tank reactor can be used in which the catalyst is present.
  • the solution of the reactant(s), water, optionally comprising solvent and the oxidant (oxygen and/or hydrogen peroxide) are added continuously.
  • oxygen oxygen is used as oxidant, it can be added in excess, off-gas can then be taken out continuously.
  • oxygen can be added in an amount to replenish the consumed oxygen.
  • the liquid reaction product can be taken off continuously through a filter in order to keep the catalyst in the reactor.
  • both the solution of reactant(s) and the oxidant are continuously fed to a trickle bed reactor containing the catalyst.
  • the gas in case oxygen is used as oxidant
  • the liquid back to the reactor in order to achieve the desired conversion of reac- tant(s) and/or oxygen (in case oxygen is used as oxidant).
  • the process according to the invention is carried out in a continuous mode.
  • the process of the invention leads to selectivities of the alpha, beta unsaturated aldehyde(s) (based on the alcohol of general formula (II)) in the range of over 90%, preferably over 93%, preferably over 95%, preferably over 97% more preferably over 99%.
  • the process according to the invention is conducted until a conversion of the alcohol of general formula (II) in the range of 10 to 99.99%, preferably in the range of 30 to 95%, and most preferably in the range of 50 to 80% is obtained.
  • the process according to the invention is performed at a temperature in the range from 1 to 250 °C, preferably in the range from 5 to 150 °C, preferably in the range from 20 to 100 °C, in the range from 20 °C to 70 °C, more preferably in the range from 25 °C to 80 °C, preferably in the range from 30 to 70°C and more preferably in the range of 35 to 50 °C.
  • the process is performed at a temperature in the range of 40 to 80 °C.
  • the obtained crude product(s) may be subjected to conventional purification measures, including distillation or chromatography or combined measures.
  • Suitable distillation devices for the purifi cation of the product(s) include, for example, distillation columns, such as tray columns optionally equipped with bubble cap trays, sieve plates, sieve trays, packages or filler materials, or spinning band columns, such as thin film evaporators, falling film evaporators, forced circulation evapora- tors, wiped-film (Sambay) evaporators, etc. and combinations thereof.
  • the sample was then washed three times with THF and hexane without contacting air.
  • the product was then dried under vacuum for 2 h and transferred to the glove box.
  • the product was placed into silica tubes, which were sealed under vacuum and then annealed at 400 °C for 6h.
  • the resulting PtBi-KCI powders were analyzed with PXRD as described below. P-XRD analysis confirmed the IMC structure.
  • the KCI containing powders were then mixed with water and centrifuged until the solution did not contain any chloride (AgNC test of the wash solution). PVP was then added and the solution was ultrasonicated.
  • aluminium oxide gamma-A Os strands with a mean diameter of 1 .5 mm (commercially available from Exacer s.r.l. Italy
  • the distribution of the catalytically active metal Pt was determined with SEM-EDXS in a cross section of the strands: the majority of the Pt was located within 100 pm from the outer surface of the catalyst.
  • the resulting catalyst was examined with XPS as described below. The XPS anal- ysis confirmed the IMC structure.
  • the sample was then washed three times with THF and hexane without contacting air.
  • the product was then dried under vac- uum for 2 h and transferred to the glove box.
  • the product was placed into silica tubes, which were sealed under vacuum and then annealed at 400 °C for 6h.
  • the resulting Pt2Bi3-KCI powders were analyzed with PXRD as described below. P-XRD analysis confirmed the IMC structure.
  • the KCI containing powders were then mixed with water and centrifuged until the solution did not contain any chloride (AgNCh test of the wash solution). PVP was then added and the solution was ultrasonicated.
  • aluminium oxide gamma-AhOs strands with a mean diameter of 1 .5 mm (commercially available from Exacer s.r.l. Italy
  • the distribution of the catalytically active metal Pt was determined with SEM-EDXS in a cross section of the strands: the majority of the Pt was located within 100 pm from the outer surface of the catalyst.
  • the resulting catalyst was examined with XPS as described below. The XPS analysis confirmed the IMC structure.
  • the sample was then washed three times with THF and hexane without contacting air.
  • the product was then dried under vacuum for 2 h and transferred to the glove box.
  • the product was placed into silica tubes, which were sealed under vacuum and then annealed at 400 °C for 6h.
  • the resulting PtBh-KCI powders were ana- lyzed with P-XRD as described below.
  • P-XRD analysis confirmed the IMC structure.
  • the KCI containing powders were then mixed with water and centrifuged until the solution did not contain any chloride (AgNC>3 test of the wash solution). PVP was then added and the solution was ultrasonicated.
  • aluminium oxide gamma-AhOs strands with a mean diameter of 1 .5 mm
  • the distribution of the catalytically active metal Pt was determined with SEM-EDXS in a cross section of the strands: the majority of the Pt was located within 100 pm from the outer surface of the catalyst.
  • the resulting catalyst was examined with XPS as described below. The XPS analysis confirmed the IMC structure.
  • the Pt-Bi materials were analyzed regarding their phase purity and structure with XRD using a Bruker D8 Advance diffractometer from Bruker AXS GmbH, Düsseldorf equipped with a Lynxeye XE 1 D-Detector, using variable slits, from 10° to 90° 2theta.
  • the anode of the X-ray tube consisted of copper.
  • a nickel filter was used to suppress the Cu radiation.
  • XPS analysis was performed with a Phi Versa Probe 5000 spectrometer using monochromatic Al Ka radiation (50.4 W) with a spot size of 200x200 pm in standard configuration.
  • the instrument work function was calibrated to give a binding energy (BE) of 84.00 eV for the Au 4f7/2 line of metallic gold and the spectrometer dispersion was adjusted to give a BE of 932.62 eV for the Cu 2p3/2 line of metallic copper.
  • the built in Phi charge neutralizer system was used on all speci- mens. To minimize the effects of differential charging, all samples were mounted insulated against ground. Survey scan analyses were carried out with a pass energy of 1 17.4 eV and an energy step size of 0.5 eV.
  • GC-Column RTX-200 (60 m (Length), 0.32 mm (ID), 1 .0 pm (Film))
  • a double jacketed reactor (length: 41 cm, internal diameter: 15 mm) was charged with 8 g of catalyst obtained according to example C1 .
  • the remaining reactor volume was filled with inert material (glass spheres, 5 mm in diameter, to a height of about 10.5 cm at the bottom of the reactor and to a height of 7.5 cm at the top of the reactor).
  • a 270 mL stirred-vessel was filled with a 150 g mixture of 3-Methyl-2-buten-1 -ol and water (composition see Table 1 ) and the mixture was metered through the reactor by using a metering pump at a flow rate of 12 kg/h.
  • the reactor temperature was adjusted at 50°C using a thermostat and set under constant 0 2 pressure of 2 bar (0 2 flow set a 20 l/h). Samples were taken hourly from the stirred- vessel and the mixture was quantitatively analyzed by GC using dioxane as internal standard. Table 1 sums up the results after 4 hours of reaction time. Conversion and selectivity are based on the weight percentages of all detected components as determined by GC. 3-Methyl-2-buten- 1 -ol (“Prenol”) was obtained from BASF.

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Abstract

L'invention concerne la préparation d'aldéhydes alpha, bêta insaturés par oxydation d'alcools en présence d'une phase liquide, la phase liquide contenant 0,1 à moins de 25 % en poids d'eau et la phase liquide contenant au moins 25 % en poids d'alcool(s) de formule générale (II) et d'aldéhyde(s) alpha, bêta insaturé(s) de formule générale (I) et l'oxydant étant de l'oxygène et/ou du peroxyde d'hydrogène et le catalyseur comprenant au moins un composé intermétallique.
PCT/EP2019/073048 2018-09-07 2019-08-29 Procédé de préparation d'aldéhydes alpha,bêta-insaturés par oxydation d'alcools en présence d'une phase liquide WO2020048855A1 (fr)

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CN114380677A (zh) * 2020-10-16 2022-04-22 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法

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CN114380677A (zh) * 2020-10-16 2022-04-22 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法
CN114380677B (zh) * 2020-10-16 2023-12-19 万华化学集团股份有限公司 一种3-甲基-2-丁烯醛的制备方法

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