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US-12616959-B2 - Production of allyl alcohol from glycerol using a reusable catalyst made from rhenium

US12616959B2US 12616959 B2US12616959 B2US 12616959B2US-12616959-B2

Abstract

The present invention relates to the use of a catalyst made of rhenium oxide supported by cerium oxide, with formula ReO x /CeO 2 (I), for catalyzing the deoxydehydration of glycerol to allyl alcohol, the reaction being carried out under 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.

Inventors

  • Benjamin Katryniok
  • Karen SILVA
  • Marcia ARAQUE

Assignees

  • CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE
  • Centrale Lille Institut
  • Université de Lille

Dates

Publication Date
20260505
Application Date
20210324
Priority Date
20200327

Claims (14)

  1. 1 . A process for catalyzing the deoxydehydration of glycerol into allyl alcohol, comprising reacting glycerol and a catalyst consisting of rhenium oxide supported by cerium, with the formula ReO x /CeO 2 (I), said process being carried out under heterogeneous conditions in the presence of at least one aliphatic alcohol.
  2. 2 . The process according to claim 1 , wherein said at least one aliphatic alcohol is used as a solvent.
  3. 3 . The process according to claim 1 , wherein said catalyst with the formula (I) is selected from the catalysts in which the amount of ReO x ranges from 2 to 20% by weight with respect to the total weight of catalyst with the formula (I).
  4. 4 . A process for producing allyl alcohol from glycerol in the presence of a catalyst, said process comprising only one step of deoxydehydration of glycerol, said process being carried out under heterogeneous conditions, in the presence of i) a catalyst consisting of rhenium oxide supported on cerium oxide, with the formula ReO x /CeO 2 (I) and (ii) at least one aliphatic alcohol.
  5. 5 . The process according to claim 4 , wherein the catalyst with the formula (I) is selected from catalysts in which the amount of ReO x ranges from 2 to 20% by weight based on the total weight of catalyst with the formula (I).
  6. 6 . The process according to claim 4 , wherein the catalyst with the formula (I) is selected from catalysts in which the amount of ReO x ranges from 3% to 15% by weight with respect to the total mass of catalyst with the formula (I).
  7. 7 . The process according to claim 4 , wherein the aliphatic alcohol is a monohydric alcohol having from 6 to 10 carbon atoms.
  8. 8 . The process according to claim 4 , wherein the aliphatic alcohol is a monohydric alcohol having from 6 to 8 carbon atoms.
  9. 9 . The process according to claim 4 , wherein the aliphatic alcohol is a monohydric secondary alcohol.
  10. 10 . The process according to claim 4 , wherein the aliphatic alcohol is 2-hexanol or 3-octanol.
  11. 11 . The process according to claim 4 , wherein the deoxydehydration reaction is carried out at a temperature greater than or equal to 140° C.
  12. 12 . The method according to claim 4 , wherein the specific surface area of the cerium oxide used for supporting ReO x ranges from about 100 m 2 /g to 300 m 2 /g as determined by the BET method.
  13. 13 . The process according to claim 6 , wherein the catalyst with the formula (I) is selected from catalysts in which the amount of ReO x ranges from 4% to 12% by weight with respect to the total mass of catalyst with the formula (I).
  14. 14 . The method according to claim 4 , wherein the specific surface area of the cerium oxide used for supporting ReO x ranges from 150 m 2 /g to 250 m 2 /g as determined by the BET method.

Description

The present invention relates to the use of supported heterogeneous catalysts containing rhenium for the production of allyl alcohol from glycerol and to a method for producing allyl alcohol from glycerol in the presence of such heterogeneous catalysts. Allyl alcohol is known as a valuable material in the chemical industry. Allyl alcohol can be used as such, but also as a raw material for producing a variety of high tonnage chemicals such as acrolein, acrylic acid or acrylonitrile. Allyl alcohol is also used as an allylating agent in modern organic chemistry (Sundararaju et al, Chem. Soc. Rev., 2012, 41, 4467-4483). At present, allyl alcohol is obtained by selective hydrogenation of acrolein which is itself most conventionally resulting from a process of selective oxidation of propylene. Glycerol is one of the most important renewable platform molecules, because same is a co-product of the transesterification process for biodiesel production (about 100 kg of glycerol are produced per ton of biodiesel). The recent expansion of the biodiesel market has led to an overabundance of glycerol, which makes same very attractive as a substrate for the synthesis of more valuable chemicals. Efficient processes of converting glycerol into useful chemicals are intensively studied around the world therefore. 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 biosourced glycerol, thus coming from a renewable resource, has never been carried out in practice. In addition, such reactions generally require catalysts. Different processes of synthesizing allyl alcohol from glycerol using rhenium-containing catalysts have been reported. E.g. Canale et al. (Catal. Sci. Technol., 2014, 4, 3697-3704) report that the deoxydehydration of glycerol into allyl alcohol is catalyzed by rhenium derivatives, either in pure glycerol or in the presence of solvents (in particular alcohols), under an air atmosphere or under hydrogen sparging. 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 to allyl alcohol with yields of 20% and 64%, respectively, using ReO3 as catalyst. However, said catalysts exhibit significant deactivation after a single test. Moreover, MTO is not easy to recover after use because same is dissolved in the liquid phase (homogeneous catalyst). Some attempts have also been made to use supported heterogeneous catalysts for carrying out the conversion of glycerol into allyl 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 e.g. Sanchez et al., Appl. Catal. B: Environmental 2014, 152-153, 117-128). However, according to such processes, the allyl alcohol yields are limited to 32% (Wang et al., Chem. J. Chin. Univ. 2013, 34, 650-655). Application EP3124462 also describes a process of direct deoxydehydration of glycerol into allyl alcohol, using a heterogeneous catalyst containing alumina-supported rhenium oxide with the formula ReO3/Al2O3, in the presence of at least one aliphatic alcohol. However, there is still a need for an improved process for the production of allyl alcohol from glycerol, with very good productivity. The present invention addresses said problem: the process according to the invention aims to produce allyl alcohol from glycerol, with a high yield and a very good productivity. Such process uses a heterogeneous catalyst rhenium on a cerium oxide support with the formula ReOx/CeO2. A first subject matter of the present invention is thus the use of a catalyst containing rhenium supported by cerium oxide with the formula ReOx/CeO2 (I), for catalyzing the deoxydehydration of glycerol into allyl alcohol, said reaction being carried out under heterogeneous conditions and in the presence of at least one aliphatic alcohol. The catalysts with the above formula (I) can be used for carrying out the deoxydehydration of glycerol into allyl alcohol on a practical scale with a yield of up to about 90%, i.e. say much higher than with the supported iron oxide catalysts of the prior art. Moreover, such catalysts can be used for carrying out such reaction with a much better productivity than the catalysts with the formula ReO3/Al2O3. Finally, the catalysts with the formula (I) can be reused and be easily recovered from the reaction mixture. Among the catalysts with the formula (I) above, the catalyst in which the amount of ReOx varies from 2% to 20% by weight with respect to the total mass of catalyst with the formula (I) are preferred, more particularly, the catalysts in which the amount of ReOx varies from 3% to 15% by weight, and preferentially from 4% to 12% by weight. As an example, the catalysts with the above fo