EP4126347A1

EP4126347A1 - Production of allyl alcohol from glycerol using a reusable catalyst made from rhenium

Info

Publication number: EP4126347A1
Application number: EP21713045.9A
Authority: EP
Inventors: Benjamin Katryniok; Karen SILVA; Marcia ARAQUE
Original assignee: Centre National de la Recherche Scientifique CNRS; Universite Lille 2 Droit et Sante; Ecole Centrale de Lille
Current assignee: Centre National de la Recherche Scientifique CNRS; Universite Lille 2 Droit et Sante; Ecole Centrale de Lille
Priority date: 2020-03-27
Filing date: 2021-03-24
Publication date: 2023-02-08
Also published as: US20230112595A1; FR3108532B1; WO2021191249A1; FR3108532A1

Abstract

The present invention relates to the use of a catalyst made from rhenium oxide supported by cerium oxide, of formula ReOx/CeO2 (I), for catalysing the deoxydehydration of glycerol to allyl alcohol, the reaction being carried out in heterogeneous conditions in the presence of at least one aliphatic alcohol; and to a method for producing allyl alcohol from glycerol in the presence of the catalyst.

Description

DESCRIPTION

Production of allyl alcohol from glycerol using a reusable rhenium-based catalyst

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).

Currently, 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.

Therefore, processes for efficiently converting glycerol into useful chemicals are being studied extensively around the world. In particular, the processes of converting allyl alcohol into acrolein and / or acrylic acid are well established, but the efficient and sustainable generation of allyl alcohol from bio-based glycerol, therefore from a renewable resource, has never been carried out in a practical manner. In addition, these reactions generally require catalysts.

Various processes for the synthesis of allyl alcohol from glycerol using rhenium-based catalysts have been reported. For example, Canale et al. (Catal. Sci. Technol., 2014, 4, 3697-3704) report that deoxydehydration of glycerol to allyl alcohol is catalyzed by rhenium derivatives, either in pure glycerol or in the presence of solvents (in particular alcohols), under air atmosphere or under hydrogen bubbling. In particular, the reaction carried out at 140 ° C in air, using 1 - hexanol or 2,4-dimethyl-3-pentanol as solvents, led to allyl alcohol with yields of 28% and 61%, respectively using methyltrioxorhenium (MTO) as catalyst, and allyl alcohol with yields of 20% and 64%, using Re03 as catalyst, respectively. However, these catalysts show significant deactivation after a single run. In addition, MTO is not easy to recover after use because it is dissolved in the liquid phase (homogeneous catalyst).

Some attempts have also been made to use heterogeneous supported catalysts to effect the conversion of glycerol to allylic alcohol. In particular, there are numerous reports on the synthesis of allyl alcohol from glycerol using solid iron oxide catalysts supported in the gas phase (see for example Sanchez et al., Appl. Catal. B: Environmental 2014, 152-153, 117-128). However, according to these methods, the yields of allyl alcohol are limited to 32% (Wang et al., Chem. J. Chin. Univ. 2013, 34, 650-655).

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.

However, there is still a need for an improved process for producing allyl alcohol from glycerol, exhibiting very good productivity.

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.

Among the 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.

By way of example, 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%.

According to a preferred embodiment of the process of the invention, 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.

According to a preferred embodiment of the invention, 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.

According to a preferred embodiment of the present invention, the aliphatic alcohol is a monohydric alcohol having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

Among the monohydric alcohols having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, secondary alcohols are preferred.

Among these secondary alcohols, mention may be made of 2-hexanol and 3-octanol.

According to a particular and preferred embodiment of the present invention, 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.

According to a preferred embodiment of the process of 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%.

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.

After reaction, 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. Preferably, as indicated above, 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).

The present invention is illustrated by the following examples, to which it is, however, not limited.

Example 1 Preparation of a catalyst based on rhenium oxide supported on cerium (ReO _x / Ce0 ₂ ) according to the invention

Rhenium catalysts supported on cerium (HAS-5, marketed by SOLVAY) were prepared by the incipient moisture impregnation method. The BET surface area of HAS-5 is 246 m ² / g. For the preparation of 10% by weight of ReO _x / CeC> 2 (ie comprising 10% by weight of ReO _x relative to the total weight of catalyst), firstly, CeC> 2 (HAS-5, 2 g) 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. After that, it was added to a dilute aqueous solution of HReC> 4, which was obtained by mixing 400 mg of the 75 wt% aqueous solution of HReC (Aldrich) with water (0.75 ml) . The impregnated catalyst was dried at 110 ° C for 12 h and calcined in static air at 500 ° C for 3 h using a heating rate of 5 ° C / min.

Example 2: Reaction of aliverol to give allyl alcohol using

10% by weight of ReO / CeC? 2 catalyst according to the invention (Mother use of the catalyst)

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. Although 2-hexanol has a boiling point of 136 ° C at atmospheric pressure, the preferred reaction temperature is above 136 ° C. After reaction, 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.

The results are in Table 1. The yield of allylic alcohol was 54%, the conversion of glycerol was 74%, and the selectivity to allylic alcohol was 73%.

Table 1. Results of the reaction of glycerol to allylic alcohol using 10% by weight of ReO _x / CeC> 2 in 2-hexanol [al [Table 1]

[a] Reaction conditions: glycerol (92 mg, 1 mmol), catalyst (100 mg) and 2-hexanol (3.3 ml), oil bath at 175 ° C, 1300 rpm, 2 h, unless indicated contrary

[c] Selectivity and conversion determined by GC analysis

[d] Efficiency = Selectivity ^* Conversion / 100

^* comprising 10% by weight of ReO _x relative to the total weight of catalyst.

Example 3 Reaction of glycerol to give allyl alcohol using 10% by weight of Re0 _x / Ce0 ₂ catalyst according to the invention ( ^2nd use of catalyst) (experiment 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)

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%.

Results:

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.

Example 5: Reaction of glycerol to give allylic alcohol using CeOi (HAS-5) (comparative)

The reaction proceeded as for Example 2, but using CeC> 2 (HAS-5, 100 mg) and 2.5 hr reaction time.

The yield of allylic alcohol was 0%, the conversion of glycerol was 3%, and the selectivity to allylic alcohol was 0%.

Example 6: Reaction of glycerol to give allylic alcohol using

2.5% by weight of ReOx / CeC 2 catalyst according to the invention (ie comprising 2.5% by weight of ReQ _x relative to the total weight of catalyst)

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 reaction proceeded as for Example 2, but using 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, 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 8: Reaction of aliverol to give allylic alcohol using

10% by weight of ReQ _x / CeC 2 catalyst according to the invention (ie comprising 10% by weight of ReQ _x relative to the total weight of catalyst) at an increased reaction time

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)

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%.

Results:

_{ReO x} charge optimization experiments were performed (Table 2): the yield of the bare CeC> 2 support was 0%, the yields increased with increasing ReO _x charge up to 10% by weight (77%, 84% and 86% for 2.5% by weight, 5% by weight and 10% by weight of ReO _x , respectively), but the yield decreased slightly for 15% by weight of ReO _x / CeC> 2 (yield 81%). Table 2. Screening of the rhenium feed on the catalyst according to the invention

ReQ _x / CeQ2 [al

[Table 2] [a] Reaction conditions: glycerol (92 mg, 1 mmol), catalyst (100 mg) and 2-hexanol (3.3 ml), oil bath at 175 ° C, 1300 rpm, 2.5 h, unless otherwise stated

[b] Selectivity for allyl alcohol and conversion of glycerol determined by GC analysis

[c] Efficiency = Selectivity ^* Conversion / 100

^* by weight of ReO _x relative to the total weight of catalyst.

Example 10: Reaction of glycerol to give allylic alcohol using 3-octanol

The reaction proceeded as for Example 2, but using 3-octanol (3.3ml) and 2.5h reaction time.

The yield of allyl alcohol was 80%, the conversion of glycerol was> 99%, and the selectivity to allyl alcohol was 80%.

Example 11: Reaction of glycerol to give allylic alcohol using 2-pentanol

The reaction proceeded as for Example 2, but using 2-pentanol (3.3ml) and 2.5h reaction time.

The yield of allyl alcohol was 65%, the conversion of glycerol was 82%, and the selectivity to allyl alcohol was 79%.

Example 12: Reaction of glycerol to give allylic alcohol using 1-heptanol

The reaction proceeded as for Example 2, but using 1-heptanol (3.3ml) and 2.5h reaction time.

The yield of allylic alcohol was 22%, the conversion of glycerol was 45%, and the selectivity to allylic alcohol was 48%.

Example 13: Reaction of glycerol to give allylic alcohol using 2-butanol

The reaction proceeded as for Example 2, but using 2-butanol (3.3ml) and 2.5h reaction time. The yield of allylic alcohol was 24%, the conversion of glycerol was 37%, and the selectivity to allylic alcohol was 65%.

Example 14 Reaction of Alvercerol to Give Allylated Alcohol Using Cvclohexanol

The reaction proceeded as for Example 2, but using cyclohexanol (3.3ml) and 2.5h reaction time.

The yield of allylic alcohol was 21%, the conversion of glycerol was 35%, and the selectivity to allylic alcohol (yield / conversion) was 59%.

Results:

Various alcohols were tested with the catalyst at 10% by weight ReO _x / CeC> 2 (Table 3). Secondary alcohols showed higher yields than primary alcohols (Table 3, Examples 8, 10-13). Aliphatic alcohol having longer chains also showed good reactivity giving allyl alcohol with a yield of 80% (Table 3, Example 10). Short chain aliphatic alcohols are good candidates if one is concerned about cost, but the reactivity is lower than in the case of 2-hexanol (Table 3, Example 13, 24% yield in the case of 2- butanol). Cyclic alcohol showed moderate yield (Table 3, Example 14).

Table 3. Screening of alcohols with 10% by weight of ReOx / CeO catalyst? according to the invention (ie comprising 10% by weight of ReQ _x relative to the total weight of catalyst) lil

[Table 3] [a] Reaction conditions: glycerol (92 mg, 1 mmol), 10% by weight of ReO _x / CeC> 2 (100 mg) and alcohol (3.3 ml), oil bath at 175 ° C, 1300 rpm, 2.5h, unless otherwise specified

[c] Yield = Selectivity ^* Conversion / 100.

Example 15: Reaction of glycerol to give allyl alcohol at 165 ° C as the temperature of the oil bath

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

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%.

Results:

Reaction temperature optimization experiments were carried out with 10% by weight of ReO _x / CeC> 2 catalyst according to the invention (Table 4). The yields increased with increasing temperature up to 175 ° C (oil bath) (62% and 86% of yields for 165 ° C and 175 ° C oil bath temperature, respectively), but the yield decreased slightly using a temperature of 185 ° C (Yield 81%).

Table 4. Screening of the reaction temperature with 10% by weight of catalyst according to the invention ReCL / CeO? (ie comprising 10% by weight of ReQ _x relative to the total weight of catalyst) fai

[Table 4]

[a] Reaction conditions: glycerol (92 mg, 1 mmol), 10% by weight of ReO _x / CeC> 2 (100 mg) and 2-hexanol (3.3 ml), 1300 rpm, 2.5h , unless otherwise stated

[c] Yield = Selectivity ^* Conversion / 100.

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

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 18: Reaction of glycerol to give allylic alcohol using

10% by weight of ReOx / CeC? 2 catalyst according to the invention with glycerol of 85% purity

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

79%, the selectivity to allylic alcohol was 79%.

Results: Glycerol at 95%, 85% and 80% purity in water was studied as a starting material for the catalytic reaction to determine the effect of water (Table 5). The yield decreased slightly when glycerol of 95% purity (Example 17) was used to give the corresponding allylic alcohol in 81% yield with complete conversion (> 99%). When glycerol of 85% and 80% purity was used (Examples 18 and 19), yields of 72% and 63% were obtained, respectively. This effect could be linked to the decrease in the boiling point of the liquid mixture when adding water to the glycerol.

Table 5. Reaction of 80-99% purity of glycerol in water using 10% by weight ReOx / CeO catalyst? according to the invention (ie comprising 10% by weight of ReQ _x relative to the total weight of catalyst) [al

[Table 5]

[a] Reaction conditions: glycerol (92 mg, 1 mmol), water (0, 5, 16, 23 mg for examples 8, 17-19 respectively), 10% by weight of ReO _x / CeC> 2 (100 mg) and 2-hexanol (3.3 ml), 175 ° C oil bath, 1300 rpm, 2.5 hrs, unless otherwise specified [b] Selectivity for allyl alcohol and conversion of glycerol determined by GC analysis

[c] Yield = Selectivity ^* Conversion / 100. Example 20: Comparison of the results obtained between the catalyst

Re0 _x / Ce0 ₂ according to the invention and the comparative ReOa / AfeOa catalyst according to EP3124462

Compared to the previous application EP3124462, the catalysts according to the invention exhibit comparable performances in terms of yield of allyl alcohol (conversion of glycerol ^* selectivity towards allyl alcohol). However, when considering 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]

From the results it can be seen that a comparable amount of allyl alcohol was produced (48.7 mg vs. 52.2 mg), but using a catalyst containing less reactive phase (5 wt% vs. 8 % by weight), whereby an increased productivity of 50% (3.9 g versus 2.6 g of allyl alcohol per gram of Re per hour) was obtained.

The ReQ _x / CeO _catalyst? according to the invention therefore makes it possible to obtain allyl alcohol from glycerol with greatly increased productivity.

Claims

1. Use of a catalyst based on rhenium oxide supported on cerium oxide of formula ReO _x / Ce0 ₂ (I), to catalyze the deoxyd dehydration of glycerol to allylic alcohol, said reaction being carried out under conditions heterogeneous in the presence of at least one aliphatic alcohol.

2. Use according to claim 1, wherein said at least one aliphatic alcohol is used as a solvent.

3. Use according to claim 1 or 2, wherein said catalyst of formula (I) is chosen from 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). ).

4. Process for the production of allyl alcohol from glycerol in the presence of a catalyst, said process comprising only a step of deoxydehydration of glycerol, said reaction being carried out under heterogeneous conditions, in the presence of i) a catalyst. rhenium oxide base supported on cerium oxide of formula ReO _x / CeC> 2 (I), and ii) at least one aliphatic alcohol.

5. Process according to claim 4, in which the catalyst of formula (I) is chosen from catalysts in which the amount of ReO _x varies from 2 to 20% by weight relative to the total mass of catalyst of formula (I). .

6. The method of claim 4 or 5, wherein the catalyst of formula (I) is chosen from catalysts in which the amount of ReO _x varies from 3% to 15% by weight, and preferably from 4% to 12%. by weight relative to the total mass of catalyst of formula (I).

7. Method according to one of claims 4 to 6, wherein the aliphatic alcohol is a monohydric alcohol having 6 to 10 carbon atoms.

8. A method according to one of claims 4 to 7, wherein the aliphatic alcohol is a monohydric alcohol having 6 to 8 carbon atoms.

9. Method according to one of claims 4 to 8, wherein the aliphatic alcohol is a monohydric secondary alcohol.

10. A method according to one of claims 4 to 9, wherein the aliphatic alcohol is 2-hexanol or 3-octanol.

11. A method according to any one of claims 4 to 10, wherein the deoxydehydration reaction is carried out at a temperature greater than or equal to 140 ° C.

12. Method according to any one of claims 4 to 11, in which 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 to 250 m ² / g by BET method.