EP4126347A1 - Production d'alcool allylique à partir de glycérol en utilisant un catalyseur réutilisable à base de rhénium - Google Patents
Production d'alcool allylique à partir de glycérol en utilisant un catalyseur réutilisable à base de rhéniumInfo
- Publication number
- EP4126347A1 EP4126347A1 EP21713045.9A EP21713045A EP4126347A1 EP 4126347 A1 EP4126347 A1 EP 4126347A1 EP 21713045 A EP21713045 A EP 21713045A EP 4126347 A1 EP4126347 A1 EP 4126347A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glycerol
- catalyst
- alcohol
- reaction
- reo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 270
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 title description 8
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 16
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003449 rhenium oxide Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 31
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 28
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 14
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 14
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- NMRPBPVERJPACX-QMMMGPOBSA-N 3-Octanol Natural products CCCCC[C@@H](O)CC NMRPBPVERJPACX-QMMMGPOBSA-N 0.000 claims description 4
- 150000003333 secondary alcohols Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000004438 BET method Methods 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 230000035484 reaction time Effects 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 10
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000012803 optimization experiment Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003281 rhenium Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
Definitions
- the present invention relates to the use of supported heterogeneous catalysts containing rhenium for the production of allylic alcohol from glycerol, as well as a process for the production of allylic alcohol from glycerol, in the presence of such heterogeneous catalysts.
- Allyl alcohol is known as a valuable material in the chemical industry. It can be used as is, but also as a raw material to produce a variety of high tonnage chemicals such as acrolein, acrylic acid or acrylonitrile. It is also used as an allylating agent in modern organic chemistry (Sundararaju et al., Chem. Soc. Rev., 2012, 41, 4467-4483).
- allyl alcohol is obtained by selective hydrogenation of acrolein, itself most conventionally resulting from a process for the selective oxidation of propylene.
- Glycerol is one of the most important renewable platform molecules, as it is a co-product of the transesterification process for the production of biodiesel (around 100 kg of glycerol is produced per tonne of biodiesel).
- the recent expansion of the biodiesel market has resulted in an overabundance of glycerol, which makes it very attractive as a substrate for the synthesis of more valuable chemicals.
- Application EP3124462 also describes a process for the direct deoxydehydration of glycerol to allylic alcohol, using a heterogeneous catalyst based on rhenium oxide on an alumina support of formula ReOs / A Os, in the presence of at least an aliphatic alcohol.
- the present invention responds to this problem: the process according to the invention aims to produce allyl alcohol from glycerol, with a high yield and very good productivity.
- This process uses a heterogeneous catalyst based on rhenium on a cerium oxide support of formula Re0 x / Ce0 2 .
- a first object of the present invention is therefore the use of a catalyst based on rhenium supported on cerium oxide of formula ReO x / CeC> 2 (I), to catalyze the deoxyd dehydration of glycerol to allylic alcohol, said reaction being carried out under heterogeneous conditions and in the presence of at least one aliphatic alcohol.
- the catalysts of formula (I) above make it possible to carry out the deoxidization of glycerol to allyl alcohol on a practical scale with a yield of up to about 90%, that is to say much higher than with the catalysts. based on supported iron oxide of the prior art. In addition, such catalysts allow to carry out this reaction with a much better productivity than the catalysts of formula Re03 / Al 2 C> 3. Finally, the catalysts of formula (I) are reusable and easily recoverable from the reaction mixture.
- catalysts of formula (I) above those in which the amount of ReO x varies from 2% to 20% by weight relative to the total mass of catalyst of formula (I) are preferred, more particularly, those in in which the amount of ReO x varies from 3% to 15% by weight, and preferably from 4% to 12% by weight.
- the catalysts of formula (I) above can in particular be prepared by impregnation at incipient humidity of cerium oxide (Ce0 2 ) with an aqueous solution of perrhenic acid (HReC> 4). After impregnation, the resulting catalyst of formula (I) is preferably dried at a temperature ranging from about 100 ° C to 150 ° C for several hours and then calcined.
- Another object of the present invention is a process for the production of allyl alcohol from glycerol in the presence of a catalyst, said process comprising only a step of dehydration of the glycerol, said reaction being carried out under heterogeneous conditions, in presence of i) a catalyst based on rhenium oxide supported on cerium oxide of formula ReO x / Ce0 2 (I) and ii) at least one aliphatic alcohol.
- the process according to the invention comprises one step, i.e. it makes it possible to obtain allyl alcohol from glycerol in a single step.
- the process according to the invention makes it possible to produce allyl alcohol without using raw materials derived from fossil resources. It is simple to perform (only one step) and very selective. This results in allyl alcohol, with yields of up to about 90%.
- the catalyst of formula (I) is chosen from catalysts in which the amount of ReO x ranges from approximately 2 to 20% by weight relative to the total mass of catalyst. of formula (I), and more particularly, those in which the amount of ReO x varies from 3% to 15% by weight, and preferably from 4% to 12% by weight.
- the specific surface of the cerium oxide used to support ReO x ranges from approximately 100 m 2 / g to 300 m 2 / g and more preferably still from 150 m 2 / g at 250 m 2 / g (BET method).
- Aliphatic alcohol is used as a solvent. Aliphatic alcohol also acts as a sacrificial reducing agent during the conversion of glycerol to allylic alcohol.
- the aliphatic alcohol is a monohydric alcohol having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.
- monohydric alcohols having 6 to 10 carbon atoms preferably 6 to 8 carbon atoms
- secondary alcohols are preferred.
- the aliphatic alcohol is 2-hexanol.
- the deoxydehydration reaction is preferably carried out at a temperature greater than or equal to approximately 140 ° C and more preferably at a temperature ranging from approximately 140 ° C to 150 ° C. A temperature of about 145 ° C. is even more particularly preferred according to the invention.
- the deoxydehydration reaction is carried out using glycerol with a purity of at least 80%, preferably at least 85%, preferably at least. at least 90%, preferably at least 95%, preferably at least 99%. More preferably, the deoxydehydration reaction is carried out using glycerol with a purity of at least 95%, preferably at least 99%.
- Example 19 As shown in Example 19 and in Table 5, the studies carried out by the inventors have shown that the use of glycerol having a purity of less than 95%, that is to say containing more than 5% by weight of impurities, in particular more than 5% by weight of water, based on the total weight of glycerol, adversely affects the yield of allylic alcohol.
- the separation of the co-products and by-products of the reaction can be carried out by any suitable technique known to those skilled in the art, for example by distillation.
- the recovery of the catalyst can be easily carried out, for example by filtration then drying. Before further use, and even if it is not mandatory, the catalyst can be calcined.
- the catalyst based on rhenium oxide supported on cerium oxide of formula ReO x / Ce0 2 (I) according to the invention is prepared by the incipient moisture impregnation method. This is illustrated in particular in Example 1. According to such a method, typically, the volume of impregnation solution (ie aqueous solution of perrhenic acid (HReC> 4)) used is equal to the pore volume of the support (CeC> 2).
- Rhenium catalysts supported on cerium were prepared by the incipient moisture impregnation method.
- the BET surface area of HAS-5 is 246 m 2 / g.
- CeC> 2 was washed with distilled water using vacuum filtration, then it was dried and calcined in static air at 110 ° C (12h) and 500 ° C (3h), respectively.
- a pressure-resistant glass tube fitted with a magnetic stir bar was loaded with glycerol (92 mg, 1 mmol, purity in water> 99%), 10% by weight ReO x / Ce0 2 (100 mg; obtained in Example 1) and 2-hexanol (3.3 ml).
- the container was sealed with a screw cap and the mixture was stirred (1300 rpm) in an oil bath maintained at 175 ° C for 2 h so that the reaction medium was maintained at a reaction temperature. 145 ° C.
- 2-hexanol has a boiling point of 136 ° C at atmospheric pressure, the preferred reaction temperature is above 136 ° C.
- the solution was cooled to room temperature and then recovered; 1 ml was taken for analysis by gas chromatography.
- Benzene (9 mg, 0.115 mmol) was added to the solution, then the mixture was mixed well. using an ultrasonic bath for 10 min at 60 ° C. Conversion and selectivity were determined by GC analysis using benzene as an internal standard.
- Example 2 The reaction proceeded as for Example 2, but using the 10% by weight of ReO x / CeC> 2 from Experiment 1 with a new amount of glycerol.
- the 10% by weight of ReO x / CeC> 2 used was reused without washing, drying or calcining beforehand.
- the yield of allylic alcohol was 54%, the conversion of glycerol was 77%, and the selectivity to allylic alcohol was 70%.
- Example 4 Reaction of glycerol to give the allylic alcohol using 10% by weight of catalyst Re0 x / Ce0 2 of the invention (3rd catalyst use) (Experiment 3)
- Example 3 The reaction proceeded as for Example 3, but using the 10% by weight of ReO x / CeC> 2 from Experiment 2 with a new amount of glycerol.
- the 10% by weight of ReO x / CeC> 2 used was reused without washing, drying or calcining beforehand.
- the yield of allylic alcohol was 58%, the conversion of glycerol was 80%, and the selectivity to allylic alcohol was 74%.
- the catalyst was easily reused to give allyl alcohol in yields of 54% and 58% for a second and a third use, respectively (Table 1, Experiments 1-3). No peak attributed to acrolein or acrylic acid was observed.
- the yield of allylic alcohol was 0%, the conversion of glycerol was 3%, and the selectivity to allylic alcohol was 0%.
- Example 2 The reaction proceeded as for Example 2, but using 2.5 wt% ReO x / CeC> 2 (100 mg) and 2.5 hr reaction time.
- the conditions for preparing the catalyst are as for Example 2, but using a dilute aqueous solution of HReC> 4, which was obtained by mixing 93 mg of the 75% by weight aqueous solution of HReC (Aldrich) with water (0.75 mL).
- the yield of allylic alcohol was 77%, the conversion of glycerol was 91%, and the selectivity to allylic alcohol was 84%.
- Example 7 Reaction of alvererol to give allylic alcohol using 5% by weight of ReO x / Ce0 2 catalyst according to the invention (ie comprising 5% by weight of ReO x relative to the total weight of catalyst)
- the conditions for preparing the catalyst are as for Example 2, but using a dilute aqueous solution of HReC, which was obtained by mixing 190 mg of the 75% by weight aqueous solution of HReC (Aldrich) with water (0.75 mL).
- the yield of allyl alcohol was 84%, the conversion of glycerol was> 99%, and the selectivity to allyl alcohol was 84%.
- Example 2 The reaction proceeded as for Example 2 using 10% by weight of ReO x / CeC> 2 (100 mg) but with 2.5 h of reaction time.
- the conditions for preparing the catalyst are as for Example 2.
- the yield of allyl alcohol was 86%, the conversion of glycerol was> 99%, the selectivity to allyl alcohol was 86%.
- Example 9 Reaction of glycerol to give allyl alcohol using 15% by weight of ReO x / Ce0 2 catalyst according to the invention (ie comprising 15% by weight of ReO x relative to the total weight of catalyst)
- Example 2 The reaction proceeded as for Example 2, but using 15 wt% ReO x / CeC> 2 (100 mg) and 2.5 hr reaction time.
- the conditions for preparing the catalyst are as for Example 2, but using a dilute aqueous solution of HReC, which was obtained by mixing 635 mg of the 75% by weight aqueous solution of HReC (Aldrich) with water (0.75 mL).
- the yield of allyl alcohol was 81%, the conversion of glycerol was> 99%, the selectivity to allyl alcohol was 81%.
- the yield of allyl alcohol was 80%, the conversion of glycerol was> 99%, and the selectivity to allyl alcohol was 80%.
- the yield of allyl alcohol was 65%, the conversion of glycerol was 82%, and the selectivity to allyl alcohol was 79%.
- the yield of allylic alcohol was 22%, the conversion of glycerol was 45%, and the selectivity to allylic alcohol was 48%.
- the yield of allylic alcohol was 21%, the conversion of glycerol was 35%, and the selectivity to allylic alcohol (yield / conversion) was 59%.
- Example 15 Reaction of glycerol to give allyl alcohol at 165 ° C as the temperature of the oil bath
- Example 2 The reaction proceeded as for Example 2, but using 165 ° C as the oil bath temperature and 2.5h reaction time.
- the yield of allylic alcohol was 62%, the conversion of glycerol was 88%, and the selectivity to allylic alcohol was 71%.
- Example 16 Reaction of glycerol to give allyl alcohol at 185 ° C as the temperature of the oil bath
- Example 2 The reaction proceeded as for Example 2, but using 185 ° C as the oil bath temperature and 2.5h reaction time.
- the yield of allyl alcohol was 81%, the conversion of glycerol was> 99%, and the selectivity to allyl alcohol was 81%.
- Example 17 Reaction of glycerol to give allylic alcohol using 10% by weight of ReOx / CeO catalyst? according to the invention with 95% purity aliverol in water
- Example 2 The reaction proceeded as for Example 2, but with a glycerol of 95% purity in water and 2.5 hours of reaction time. Glycerol (92 mg) and water (5 mg) were mixed beforehand in order to obtain a homogeneous mixture with 2-hexanol. The yield of allyl alcohol was 81%, the conversion of glycerol was> 99%, the selectivity to allyl alcohol was 81%.
- Example 2 The reaction proceeded as for Example 2, but with a glycerol of 85% purity and 2.5 hours of reaction time. Glycerol (92 mg) and water (16 mg) were mixed beforehand in order to obtain a homogeneous mixture with 2-hexanol.
- the yield of allylic alcohol was 72%, the conversion of glycerol was 91%, the selectivity to allylic alcohol was 79%.
- Example 19 Reaction of aliverol to give allylic alcohol using 10% by weight of ReO x / CeO catalyst? according to the invention with alvcerol of 80% purity
- the reaction proceeded as for Example 2, but with a glycerol of 80% purity and 2.5 hours of reaction time.
- Glycerol (92 mg) and water (23 mg) were mixed beforehand in order to obtain a homogeneous mixture with 2-hexanol.
- the yield of allyl alcohol was 63%, the conversion of glycerol was
- the catalysts according to the invention exhibit comparable performances in terms of yield of allyl alcohol (conversion of glycerol * selectivity towards allyl alcohol).
- the productivity of the catalysts one can indicate a much higher productivity for the Re0 x / Ce0 2 catalyst according to the invention, as can be seen in the following Table 6: [Table 6]
- the ReQ x / CeO catalyst? according to the invention therefore makes it possible to obtain allyl alcohol from glycerol with greatly increased productivity.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2003019A FR3108532B1 (fr) | 2020-03-27 | 2020-03-27 | Production d’alcool allylique à partir de glycérol en utilisant un catalyseur réutilisable à base de rhénium |
PCT/EP2021/057525 WO2021191249A1 (fr) | 2020-03-27 | 2021-03-24 | Production d'alcool allylique à partir de glycérol en utilisant un catalyseur réutilisable à base de rhénium |
Publications (1)
Publication Number | Publication Date |
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EP4126347A1 true EP4126347A1 (fr) | 2023-02-08 |
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ID=70978183
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP21713045.9A Pending EP4126347A1 (fr) | 2020-03-27 | 2021-03-24 | Production d'alcool allylique à partir de glycérol en utilisant un catalyseur réutilisable à base de rhénium |
Country Status (4)
Country | Link |
---|---|
US (1) | US20230112595A1 (fr) |
EP (1) | EP4126347A1 (fr) |
FR (1) | FR3108532B1 (fr) |
WO (1) | WO2021191249A1 (fr) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3124462B1 (fr) | 2015-07-30 | 2019-01-30 | Centre National De La Recherche Scientifique | Utilisation de catalyseurs supportés hétérogènes contenant du rhénium pour la deoxydehydration directe de glycérol en alcool allylique |
-
2020
- 2020-03-27 FR FR2003019A patent/FR3108532B1/fr active Active
-
2021
- 2021-03-24 US US17/907,359 patent/US20230112595A1/en active Pending
- 2021-03-24 WO PCT/EP2021/057525 patent/WO2021191249A1/fr active Application Filing
- 2021-03-24 EP EP21713045.9A patent/EP4126347A1/fr active Pending
Also Published As
Publication number | Publication date |
---|---|
FR3108532B1 (fr) | 2022-03-04 |
FR3108532A1 (fr) | 2021-10-01 |
US20230112595A1 (en) | 2023-04-13 |
WO2021191249A1 (fr) | 2021-09-30 |
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