WO2018040058A1 - Déshydratation de diols - Google Patents

Déshydratation de diols Download PDF

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Publication number
WO2018040058A1
WO2018040058A1 PCT/CN2016/097860 CN2016097860W WO2018040058A1 WO 2018040058 A1 WO2018040058 A1 WO 2018040058A1 CN 2016097860 W CN2016097860 W CN 2016097860W WO 2018040058 A1 WO2018040058 A1 WO 2018040058A1
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compound
comprised
cerium oxide
functions
oxide particles
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PCT/CN2016/097860
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English (en)
Inventor
Marc Pera Titus
Floryan De Campo
Sébastien PAUL
Fangli JING
Benjamin Katryniok
Franck Dumeignil
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Rhodia Operations
Centre National De La Recherche Scientifique
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Priority to PCT/CN2016/097860 priority Critical patent/WO2018040058A1/fr
Publication of WO2018040058A1 publication Critical patent/WO2018040058A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths

Definitions

  • the present invention concerns a method for producing an alkene.
  • the method comprises a step of converting a compound (I) comprising at least two hydroxyl functions into a compound (II) comprising at least two alkenyl functions with cerium oxide particles as catalyst.
  • Method of the present invention notably permits the production of butadiene from 1, 3-butanediol or 1, 4-butanediol.
  • 1, 3-butadiene is an important feedstock to manufacture chemicals and materials that further serve diverse industries including automotive, paints, appliance manufacturing. Its main application segments include Styrene-Butadiene Rubber (SBR) , Polybutadiene Rubber (PBR) , Styrene Butadiene Latex (SB Latex) . Chemical intermediates made from butadiene include chloroprene which is used in the manufacture of neoprene.
  • SBR Styrene-Butadiene Rubber
  • PBR Polybutadiene Rubber
  • SB Latex Styrene Butadiene Latex
  • butanediols (1, 2-, 1, 3-or 1, 4-) are used to produce allylic alcohols catalyzed by CeO 2 .
  • 1, 3-butadiene in those reactions could be got but in very low yield and selectivity.
  • Satoshi Sato et al. made a lot of researches on dehydration of butanediols over CeO 2 .
  • Catalysis communications 4 (2003) 77-81” butadiene can be obtained by dehydration of 1, 3-butanediol over commercial pure CeO 2 with specific surface area 20 or 41 m 2 /g. But the selectivity is quite poor since 1, 3-butadiene is a by-product in this reaction.
  • Catalysis communications 5 (2004) 397-400 describes dehydration reaction of 1, 4-butanediol to produce homoallyl alcohol such as 3- buten-1-ol over pure CeO 2 .
  • 1, 3-butadiene could be obtained by stepwise dehydration of 3-buten-1-ol.
  • the selectivity of 1, 3-butadiene is high when reaction is performed at 275 °C. But conversion is low, which leads to low yield.
  • the specific surface area of the CeO 2 was 20 m 2 /g by the calculation with BET method.
  • “Journal of Molecular Catalyst A: Chemical 221 (2004) 177-183” describes dehydration of butanediols over CeO 2 catalyst with different particle size range from 13-141 m 2 /g. 1, 3-butadiene is detected with low conversion and selectivity.
  • the present invention provides a method for converting a compound (I) comprising at least two hydroxyl functions into a compound (II) comprising at least two alkenyl functions, said method comprising dehydrating the compound (I) in the presence of cerium oxide particles having following properties:
  • catalytic performances of cerium oxide particles occur without any high cost and non-environmental friendly metals, such as Pd, Lu, Ni, Ag or strong acid.
  • method of the present invention permit to obtain alkene, notably dienes of interest with a high selectivity and conversion in comparison with catalysts of the prior art.
  • Conversion corresponds to the total amount of reactant (butanediol) that was converted during the reaction. Conversion may be determined for instance by the way of dividing the amount of reactant (butanediol) converted by the amount of reactant (butanediol) supplied.
  • cerium oxide is in the form of cerium oxide (CeO 2 ) .
  • specific surface area is understood to mean the BET specific surface area determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 laid down from the Brunauer-Emmett-Teller method described in the periodical “The Journal of the American Chemical Society, 60, 309 (1938) ” .
  • hydrocarbyl refers to a monovalent hydrocarbon group, i.e. a group consisting of carbon atoms and hydrogen atoms, which group is connected to the remainder of the compound of formula (I) via a carbon-to-carbon single bond and may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic.
  • a "C 1-11 hydrocarbyl” denotes a hydrocarbyl having 1 to 11 carbon atoms.
  • alkyl refers to a monovalent saturated aliphatic (i.e. non-aromatic) acyclic hydrocarbon group which may be linear or branched and does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • alkenyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon double bond while it does not comprise any carbon-to-carbon triple bond.
  • alkynyl refers to a monovalent unsaturated aliphatic acyclic hydrocarbon group which may be linear or branched and comprises at least one carbon-to-carbon triple bond and optionally one or more carbon-to-carbon double bonds.
  • cycloalkyl refers to a monovalent cyclic saturated aliphatic hydrocarbon group which does not comprise any carbon-to-carbon double bond or any carbon-to-carbon triple bond.
  • Non-limiting examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cycloalkenyl refers to a monovalent cyclic unsaturated aliphatic hydrocarbon group which comprises at least one carbon-to-carbon double bond and does not comprise any carbon-to-carbon triple bond.
  • Non-limiting examples of cycloalkyl groups are cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclohexadienyl.
  • aryl refers to a monovalent aromatic hydrocarbon group, including bridged ring and/or fused ring systems, containing at least one aromatic ring.
  • Aryl may, for example, refer to phenyl, naphthyl or anthracenyl.
  • the cerium oxide particles according to the present invention comprise at least a cerium oxide.
  • cerium oxide particles have a specific surface area (SBET) comprised from 100 to 300 m 2 /g, after calcination at 400°C for 10 hours, preferably comprised from 120 to 300 m 2 /g.
  • cerium oxide particles may have a specific surface area (SBET) comprised from 30 to 65 m 2 /g, after calcination at 900°C for 5 hours, preferably comprised from 40 to 65 m 2 /g.
  • the specific surface area referred to in the present specification is measured according to the BET method utilizing absorption of nitrogen gas, which is the most standard method for measuring the specific surface area of powders.
  • Total pore volume of cerium oxide particles may be comprised from 0.10 to 0.40 ml/g after calcination at 900°C for 5 hours, under air; preferably comprised from 0.12 to 0.28 ml/g.
  • the total pore volume may be measured by N 2 adsorption at 77.4 K at a P/P 0 value of 0.99, where P is the N 2 pressure and P 0 is the saturation vapor pressure of N 2 .
  • Cerium oxide particles may have a S1/S2 ratio comprised from 0.45 to 0.7 taken after calcination at 800°C for 2 hours. Cerium oxide particles may have a S1/S2 ratio comprised from 0.25 to 0.5 taken after calcination at 900°C for 5 hours.
  • Said S1/S2 ratio is a ratio of the area (S1) defined by a baseline and a TPR curve in a temperature range of 200 to 600°C to the area (S2) defined by said baseline and said TPR curve in a temperature range of 600 to 1000°C.
  • a higher S1/S2 ratio of a cerium oxide is expected to result in a higher oxygen absorbing and desorbing capability and higher activity to purify exhaust gas at a lower temperature.
  • the “baseline” means a line segment drawn from the point on the TPR curve corresponding to 200°C in a parallel to the axis representing temperature, up to 1000°C.
  • the TPR may be performed as described in U.S. Pat No. 7,361,322.
  • Cerium oxide particles may also comprise at least one metallic element oxide, other than cerium oxide, for instance in a proportion comprised from 1 to 40 %by weight of oxide, preferably in a proportion comprised from 1 to 20 %by weight of oxide.
  • Oxide refers there to final mixed oxide defined as integration of cerium oxide and metallic element oxide.
  • Metallic element of metallic element oxide is preferably chosen in the group consisting of:
  • rare earth elements such as La, Pr, Nd and Y, and
  • Metallic element oxides are preferably chosen in the group consisting of : lanthanum oxide (La 2 O 3 ) , praseodymium oxide (Pr 6 O 11 ) , neodymium oxide (Nd 2 O 3 ) and yttrium oxide (Y 2 O 3 ) .
  • Cerium oxide particles as described above or as obtained by means of the preparation process previously described may be in the form of powders, but they can optionally be formed so as to be in the form of granules, pellets, foams, beads, cylinders or honeycombs of variable dimensions.
  • Cerium oxide particles of the present invention provide a weight loss comprised from -1.0 to +6.0 %, between a temperature of 350°C and 1000°C, more preferably comprised from -0.5 to +5.0 %.
  • the weight loss could be measured by TGA analysis on a TA SDT Q600 Instrument with 7 mg sample. The sample is heated from ambient temperature to 1000°C under air with a heating rate of 10°C/min. The weight loss of the samples is calculated as follows.
  • Cerium oxide particles of present invention could be obtained by calcination treatment of some commercial products, such as Actalys HSA5, HSA20 from Solvay.
  • Cerium oxide particles may be produced according to the method described in U.S. Pat No. 7,361,322.
  • Cerium oxide particles may notably be obtained by a method comprising at least the steps of:
  • step (b) holding said cerium solution prepared in step (a) at a temperature form 60 to 220°C under heating,
  • a cerium solution not less than 90 mol %of which cerium ions are tetravalent is provided in step (a) .
  • the cerium solution not less than 90 mol %of which cerium ions are tetravalent may preferably be a ceric nitrate solution.
  • a ceric nitrate solution initially contains 250 g/L of cerium in terms of cerium oxide, and has an initial acid concentration of usually 0.1 to 1 N. The initial acid concentration relates to the acid concentration in the subsequent reaction. If the acid concentration is too low, the crystallinity of the precipitate to be discussed later may not be improved sufficiently, resulting in low heat resistance of the objective ceric oxide. If the acid concentration is too high, excess base is required in the neutralization reaction for precipitating cerium, thus being industrially disadvantageous.
  • the acid concentration of the cerium solution may be adjusted to usually 5 to 150 g/L, preferably 10 to 120 g/L, more preferably 15 to 100 g/L, in terms of cerium oxide, usually with water, preferably with deionized water.
  • step (b) next the cerium solution prepared in step (a) is held at 60 to 220°C under heating to cause reaction of the cerium solution in step (b) .
  • Any reaction vessel may be used in step (b) without critical limitation, and either a sealed vessel or an open vessel may be used.
  • an autoclave reactor may preferably be used.
  • the temperature for holding under heating is 60 to 220°C, preferably 80 to 180°C, more preferably 90 to 160°C, and the duration of holding under heating is usually 10 minutes to 48 hours, preferably 30 minutes to 36 hours, more preferably 1 hour to 24 hours. If the cerium solution is not sufficiently held under heating, the crystallinity of the precipitate to be discussed later may not be improved, resulting in insufficient heat resistance of the objective ceric oxide. Even if the cerium solution is held under heating for a longer time, the heat resistance may be affected little, and thus being industrially disadvantageous.
  • step (b) the heated cerium solution is usually cooled in step (c) .
  • the cerium solution may usually be cooled under stirring.
  • Means for cooling are not critical, and may be cooling in an atmosphere or forced cooling with cooling tube.
  • the cooling temperature is usually not higher than 60°C, preferably not higher than 25°C.
  • a precipitant is added to the cooled cerium solution to prepare a precipitate in step (d) .
  • the precipitant used in step (d) may be a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, an aqueous ammonia solution, ammonia gas, or mixtures thereof, with an aqueous ammonia solution being preferred.
  • the precipitant may be added by preparing an aqueous solution of the precipitant at a suitable concentration and adding the solution to the precursor solution prepared in step (c) under stirring, or when ammonia gas is used, by blowing the gas into the reaction vessel under stirring.
  • the amount of the precipitant may easily be decided by tracing the pH change of the solution. Usually, a sufficient amount is such that the pH of the solution is not lower than 7, and a preferred amount is such that the pH is 7 to 10.
  • the precipitation may also be possible by introducing the cooled cerium solution to a precipitant.
  • required amount of the precipitant is calculated and prepared in advance so that the pH after precipitation may be able to be not lower than 7.
  • a product with grown crystals may be precipitated.
  • This product is a preferable precursor for obtaining the ceric oxide of the present invention, and may be separated, for example, by Nutsche method, centrifuging, or filter pressing.
  • the precipitate may optionally be washed with water, as required. Further, the precipitate may optionally be dried to a suitable extent for improving the efficiency in the following step (e) .
  • the precipitate obtained in step (d) may be subjected to, before step (e) , step (d-1) of dispersing the precipitate in a solvent such as water, and heat-treating the resulting solution at usually 60 to 220°C, preferably 80 to 180°C, more preferably 90 to 160°C, to obtain a reprecipitate.
  • the duration of the heat treatment is usually 10 minutes to 48 hours, preferably 30 minutes to 36 hours.
  • the precipitate thus obtained is calcined in step (e) to obtain the objective ceric oxide.
  • the calcination temperature may suitably be selected from the range of usually 250 to 900°C. The selection of the temperature may be made as desired, depending on the required or guaranteed values of the specific surface area and bulk density. From a practical point of view to prepare a co-catalyst material wherein the specific surface area is important, the calcination temperature may preferably be 250 to 800°C, more preferably 250 to 700°C, most preferably 280 to 600°C. The duration of calcination may suitably be determined depending on the temperature, and may preferably be 1 to 10 hours.
  • the ceric oxide obtained may usually be pulverized.
  • the pulverization may sufficiently be performed in an ordinary pulverizer, such as a hammer mill, to obtain a powder of a desired particle size.
  • the ceric oxide obtained by the present method may be given a desired particle size through the above mentioned pulverization.
  • a metallic element compound for example a nitrate, chloride, oxide, hydroxide, carbonate, halide, oxyhalide, oxynitrate, sulfate, phosphate and/or acetate.
  • Metallic salt may be made of a cationic metal ion, notably chosen in the group consisting of:
  • rare earth elements such as La, Pr, Nd and Y, and
  • an organic texturing agent may be added to the suspension.
  • An organic texturing agent usually refers to an organic compound, such as a surfactant, able to control or modify the mesoporous structure of the cerium oxide.
  • “Mesoporous structure” basically describes a structure which specifically comprises pores with an average diameter comprised from 2 to 50 nm, described by the term “mesopores” .
  • these structures are amorphous or crystalline compounds in which the pores are generally distributed in random fashion, with a very wide pore-size distribution.
  • the organic texturing agent may be added directly or indirectly. It can be added directly to the suspension or precipitate resulting from the preceding step. It can also be first added in a composition, for instance comprising a solvent of the organic texturing agent, and said composition being then added to the suspension or precipitate as previously obtained.
  • the amount of organic texturing agent used is generally from 5 %to 100 %and more particularly from 15 %to 60 %.
  • the organic texturing agent may be adsorbed on the surface of secondary particles and primary particles of the precipitates.
  • the organic texturing agent adsorbed on the primary particles will lead to increase the size of mesopores and pore volume of the precipitate.
  • Organic texturing agents are preferably chosen in the group consisting of : anionic surfactants, nonionic surfactants, polyethylene glycols, carboxylic acids and their salts, and surfactants of the carboxymethylated fatty alcohol ethoxylate type.
  • anionic surfactants nonionic surfactants
  • nonionic surfactants polyethylene glycols
  • carboxylic acids and their salts and surfactants of the carboxymethylated fatty alcohol ethoxylate type.
  • surfactants of anionic type mention may be made of ethoxycarboxylates, ethoxylated fatty acids, sarcosinates, phosphate esters, sulfates such as alcohol sulfates, alcohol ether sulfates and sulfated alkanolamide ethoxylates, and sulfonates such as sulfosuccinates, and alkylbenzene or alkylnapthalene sulfonates.
  • ethoxycarboxylates ethoxylated fatty acids
  • sarcosinates phosphate esters
  • sulfates such as alcohol sulfates, alcohol ether sulfates and sulfated alkanolamide ethoxylates
  • sulfonates such as sulfosuccinates, and alkylbenzene or alkylnapthalene sulfonates.
  • nonionic surfactants mention may be made of acetylenic surfactants, alcohol ethoxylates, alkanolamides, amine oxides, ethoxylated alkanolamides, long-chain ethoxylated amines, copolymers of ethylene oxide/propylene oxide, sorbitan derivatives, ethylene glycol, propylene glycol, glycerol, polyglyceryl esters and ethoxylated derivatives thereof, alkylamines, alkylimidazolines, ethoxylated oils and alkylphenol ethoxylates. Mention may in particular be made of the products sold under the brands and
  • carboxylic acids it is in particular possible to use aliphatic monocarboxylic or dicarboxylic acids and, among these, more particularly saturated acids. Fatty acids and more particularly saturated fatty acids may also be used. Mention may thus in particular be made of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid and palmitic acid.
  • dicarboxylic acids mention may be made of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Salts of the carboxylic acids may also be used, in particular the ammonium.
  • lauric acid and ammonium laurate By way of example, mention may be made more particularly of lauric acid and ammonium laurate.
  • a surfactant which is selected from those of the carboxymethylated fatty alcohol ethoxylate type.
  • product of the carboxymethylated fatty alcohol ethoxylate type is intended to mean products consisting of ethoxylated or propoxylated fatty alcohols comprising a CH 2 -COOH group at the end of the chain.
  • R 1 denotes a saturated or unsaturated carbon-based chain of which the length is generally at most 22 carbon atoms, preferably at least 12 carbon atoms
  • R 2 , R 3 , R 4 and R 5 may be identical and may represent hydrogen or else R 2 may represent an alkyl group such as a CH 3 group and R 3 , R 4 and R 5 represent hydrogen
  • n is a non-zero integer that may be up to 50 and more particularly from 5 to 15, these values being included.
  • a surfactant may consist of a mixture of products of the formula above for which R 1 may be saturated or unsaturated, respectively, or alternatively products comprising both –CH 2 -CH 2 -O-and –C (CH 3 ) -CH 2 -O-groups.
  • the purity of cerium oxide particles in present invention may be at least 95%and preferably be comprised from 99%to 100%.
  • the compound (I) comprising at least two hydroxyl functions according to the present invention may notably have two hydroxyl functions.
  • the compound (I) comprising at least two hydroxyl functions according to the invention may be chosen in the group constituted by: compound of formula (I) :
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently selected from hydrogen or C 1-11 hydrocarbyl.
  • Said hydrocarbyl is preferably selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, more preferably selected from alkyl, alkenyl, alkynyl, or aryl, and even more preferably selected from alkyl, alkenyl, or aryl.
  • Said alkyl preferably comprises 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 (i.e. 1, 2, 3 or 4) carbon atoms.
  • Said alkenyl preferably comprises 2 to 11 carbon atoms, more preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 (i.e. 2, 3 or 4) carbon atoms.
  • Said alkynyl preferably comprises 2 to 11 carbon atoms, more preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 (i.e. 2, 3 or 4) carbon atoms.
  • Said cycloalkyl preferably comprises 3 to 11 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 (i.e. 3, 4, 5 or 6) carbon atoms.
  • Said aryl is preferably selected from phenyl or naphthyl, and is more preferably phenyl.
  • said C 1-11 hydrocarbyl is preferably selected from C 1-11 alkyl (in particular, C 1-6 alkyl or C 1-4 alkyl) , C 2-11 alkenyl (in particular, C 2-6 alkenyl or C 2-4 alkenyl) , C 2-11 alkynyl (in particular, C 2-6 alkynyl or C 2-4 alkynyl) , C 3-11 cycloalkyl (in particular, C 3-6 cycloalkyl) , C 3-11 cycloalkenyl (in particular, C 3-6 cycloalkenyl) , phenyl or naphthyl.
  • C 1-11 alkyl in particular, C 1-6 alkyl or C 1-4 alkyl
  • C 2-11 alkenyl in particular, C 2-6 alkenyl or C 2-4 alkenyl
  • C 2-11 alkynyl in particular, C 2-6 alkynyl or C 2-4 alkynyl
  • said C 1-11 hydrocarbyl is selected from C 1-11 alkyl (in particular, C 1-6 alkyl or C 1-4 alkyl) , C 2-11 alkenyl (in particular, C 2-6 alkenyl or C 2-4 alkenyl) or phenyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen, C 1-11 alkyl, C 2-11 alkenyl, C 2-11 alkynyl, C 3-11 cycloalkyl, C 3-11 cycloalkenyl, phenyl or naphthyl, and are more preferably each independently selected from hydrogen, C 1-6 alkyl, C 2-6 alkenyl or phenyl, and are even more preferably each independently selected from hydrogen or linear C 1-4 alkyl.
  • the compound of formula (I) , (II) and (III) comprises a total of 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, even more preferably 4 to 6 carbon atoms, and most preferably 4 carbon atoms.
  • the compound (I) comprising at least two hydroxyl functions to be used in the method according to the invention is in linear (i.e. unbranched) form.
  • the compound (I) comprising at least two hydroxyl functions is selected from a group consisting of 1, 3-butanediol, 1, 4-butanediol and 1, 2-butanediol.
  • a high purity of compound (I) may be preferred.
  • the content of the water in the compound (I) may be at most 10 vol. %, preferably at most 5 vol. %, more preferably at most 1 vol. %.
  • the content of water in the compound (I) may be comprised from 0.1 to 10 vol. %, preferably from 0.1 to 5 vol. %, more preferably from 0.1 to 1 vol. %.
  • compound (II) comprising at least two alkenyl functions may notably be a “diene” .
  • the term “diene” refers to a compound comprising two carbon-to-carbon double bonds and, in particular, refers to a compound of formula (IV) :
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings and preferred meanings as described and defined herein above for the compound of formula (I) , (II) and (III) .
  • the compound (I) comprising at least two hydroxyl functions is 1, 3-butanediol or 1, 4-butanediol and the produced compound (II) comprising at least two alkenyl functions is 1, 3-butadiene.
  • the conversion of compound (I) comprising at least two hydroxyl functions reaches at least 65 %
  • the selectivity of compound (II) comprising at least two alkenyl functions could reaches at least 2 %.
  • the conversion of compound (I) may be comprised from 70 %to 100 %and more preferably comprised from 90 %to 100 %when above mentioned cerium oxide catalyst is employed.
  • the selectivity of compound (II) may be comprised from 30 %to 80 %and more preferably comprised from 50 %to 70 %when above mentioned cerium oxide catalyst is employed.
  • the selectivity of compound (II) may be comprised from 30 %to 80 %when conversion of compound (I) is comprised from 70 %to 100 %.
  • the method to improve the conversion is not particularly limited. Any reaction condition lead to high conversion could be considered. People having ordinary skill in the art could realize high conversion by employing proper parameters, such as reaction temperature, reaction time, amount of catalyst, solvent or even using proper equipment.
  • Selectivity corresponds to transformation of the reactant (butanediol) to the desired product divided by the overall conversion of the reactant (butanediol) .
  • Selectivity may be determined for instance by the way of dividing the number of moles of the desired product by the total amount of moles of all products obtained (desired and undesired products) .
  • the method for producing an alkene of present invention usually comprises at least the following steps:
  • the mixture of compound (I) comprising at least two hydroxyl functions and catalyst is reacted at a temperature range usually comprised from 50 °C to 500 °C, preferably from 300 °C to 450 °C.
  • the method of producing a compound (II) comprising at least two alkenyl functions by dehydration of a compound (I) comprising at least two hydroxyl functions occurs in a single step.
  • a single step according to the invention means that no intermediate products have to be isolated or that several components have to be produced in separate process steps.
  • the present invention can be considered as "one pot" procedure, i.e. the catalyst and the compound (I) are mixed and brought into contact with each other so that the reaction for producing compound (II) can be started.
  • non-oxidizing atmosphere means any atmosphere that excludes oxygen and does not lead to the formation of undesirable side reaction products such as CO 2 .
  • Suitable non-oxidizing atmospheres which can be provided are, for example, inert gases such as N 2 , He, Ne or Ar.
  • the dehydration reaction is preferably carried out in a dried atmosphere, meaning an atmosphere comprising from 0.1 to 5 vol. %of water in a liquid or gaseous phase.
  • the dehydration reaction could also be conducted in the liquid phase, depending on the starting materials and other reaction conditions.
  • the pressure of the dehydration reaction is not particularly limited, and suitable pressures would be understood to and can be determined by those of ordinary skill in the art.
  • the dehydration reaction may be, but is not limited to, conducted at a total pressure of about 1 bar to about 20 bar, such as about 5 bar to about 20 bar or 10 bar to about 20 bar or about atmospheric pressure.
  • the reactor type which may be used in the present invention is not particularly limited, and suitable reactor types would be understood to and can be determined by those of ordinary skill in the art.
  • the reactor may have a simple design or may be complex.
  • the type of reactor may be chosen by the skilled person depending on the components used in the process and the products which should be specifically obtained.
  • the dehydration reaction may be, but not limited to, conducted in a flow reactor or in a fluid or fluidized bed reactor.
  • the flow reactor is not particularly limited, and suitable flow reactors would be understood to and can be determined by those of ordinary skill in the art.
  • the flow reactor may be a fixed bed reactor, a up flow fixed bed reactor, or a down flow fixed bed reactor.
  • the fixed bed reactor may be isothermal and/or adiabatic.
  • Reaction may be carried out in a batch type reactor or in a continuous reactor. Preferably, the reaction is carried out in a continuous fixed-bed reactor.
  • the contact time could be comprised from 0.06 g h cm -3 to 0.40 g h cm -3 and preferably from 0.10 g h cm -3 to 0.20 g h cm -3 .
  • the alkene as produced may be isolated and purified with known methods, such as for instance solvent extraction, distillation, pressure swing adsorption (PSA) or separation film method.
  • known methods such as for instance solvent extraction, distillation, pressure swing adsorption (PSA) or separation film method.
  • Cerium oxide (Actalys HSA5) was calcined in the air at 400°C for 10 hours to obtain cerium oxide powder.
  • the obtained oxide powder was measured of the specific surface area by the BET method and of the weight loss by the TG method.
  • the specific surface area is measured by N 2 adsorption isotherms at 77 K using a Micromeritics ASAP 2010 Surface Area Analyzer using 100 mg sample.
  • the surface areas were calculated by the Brunauer-Emmett-Teller (BET) method.
  • the weight loss is measured by TGA analysis on a TA SDT Q600 Instrument with 7 mg sample. The sample is heated from ambient temperature to 1000°C under air with a heating rate of 10°C/min. The weight loss of the samples is calculated as follows.
  • the specific surface area is 154.7m 2 /g and weight loss is +4.6%as measured by above mentioned method.
  • the lighter products such as BDO and propylene (PLE) were analyzed online using a GC equipped with two semi-capillary columns (WAX plus: 0.53 mm i.d., 30 m length; and Porapak Q: 0.53 mm i.d., 30 m length) and a flame ionization detector (FID) .
  • WAX 0.53 mm i.d., 30 m length
  • Porapak Q 0.53 mm i.d., 30 m length
  • FID flame ionization detector
  • Heavier products such as methyl ethyl ketone (MEK) , methyl vinyl ketone (MVK) , 2-butanol, 1-butanol, 3-buten-2-ol (3B2ol) and 3-buten-1-ol (3B1ol) were condensed in a cold trap and further analyzed using an offline GC-FID equipped with a semi-capillary column (EC1000: 0.53 mm i.d., 30 m length) . The reaction data were collected after 8 h stabilization to ensure that the reaction attained the steady state. The reaction performed under different temperatures in vaporization chamber is shown in Table 1.
  • Cerium oxide catalyst (Actalys HSA20) was calcined in the air at 400°C for 10 hours to obtain cerium oxide powder.
  • the specific surface area is 129.9m 2 /g and weight loss is -0.4%as measured by same measurement method of Example 1.
  • Ceria catalyst (Actalys HSA20) is used in this example to convert 1, 3-butanediol (BDO) into 1, 3-butadiene (BD) , which is performed under the same reaction condition of Example 1.
  • BDO 1, 3-butanediol
  • BD 1, 3-butadiene

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Abstract

L'invention concerne un procédé de production d'un alcène. Le procédé comprend une étape de conversion d'un composé (I) comprenant au moins deux fonctions hydroxyle en un composé (II) comprenant au moins deux fonctions alcényle avec des particules d'oxyde de cérium comme catalyseur. Elle permet notamment la conversion de 1,3-butanediol,1,4-butanediol en butadiène.
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CN112645787A (zh) * 2019-10-11 2021-04-13 中国科学院大连化学物理研究所 一种制备异戊二烯的方法

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CN105164089A (zh) * 2013-02-04 2015-12-16 安迪苏法国联合股份有限公司 通过催化转化至少一种醇来制备烯烃的方法
CN105452204A (zh) * 2013-09-12 2016-03-30 东丽株式会社 丁二烯的制造方法
WO2016092063A1 (fr) * 2014-12-12 2016-06-16 Versalis S.P.A. Procédé de production de 1,3-butadiène à partir de 1,3-butanediol
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CN111320531B (zh) * 2018-12-13 2023-07-28 中国石油化工股份有限公司 一种羟基酮类化合物的制备方法
CN112645787A (zh) * 2019-10-11 2021-04-13 中国科学院大连化学物理研究所 一种制备异戊二烯的方法
CN112645787B (zh) * 2019-10-11 2022-03-08 中国科学院大连化学物理研究所 一种制备异戊二烯的方法

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