Process for transformation of a feedstock comprising a lignocellulosic biomass using an acidic homogeneous catalyst in combination with a heterogeneous catalyst comprising a specific substrate

Patent metadata

Field	Value
Publication number	US-9809504-B2
Application number	US-201514862296-A
Country	US
Kind code	B2
Filing date	Sep 23, 2015
Priority date	Sep 26, 2014
Publication date	Nov 7, 2017
Grant date	Nov 7, 2017

Abstract

Process for transformation of a feedstock of lignocellulosic biomass and/or the carbohydrates, into mono-oxidized or poly-oxidized compounds, wherein the feedstock is contacted, simultaneously, with a catalytic system that comprises one or more homogeneous catalysts selected from Brønsted acids and heterogeneous catalysts comprising at least one metal selected from groups 6 to 11 and 14 of the periodic table, and a substrate selected from perovskites of formula ABO 3 , in which A is Mg, Ca, Sr, Ba, and La, and B is selected from Fe, Mn, Ti and Zr, oxides of lanthanum, neodymium, yttrium, cerium, and niobium, or mixtures thereof, and mixed oxides of aluminates of zinc, copper, and cobalt, or mixtures thereof, in the same reaction chamber, with at least one solvent, being water or water with at least one other solvent, under reducing atmosphere, and temperature of 50° C. to 300° C., and pressure of 0.5 MPa to 20 MPa.

First claim

The invention claimed is:

1. A process for transformation of a feedstock that is selected from among a lignocellulosic biomass and carbohydrates, by themselves or in a mixture, into mono-oxidized or poly-oxidized compounds, in which said feedstock is brought into contact, simultaneously, with a catalytic system that comprises one or more homogeneous catalyst(s) and one or more heterogeneous catalyst(s), in the same reaction chamber, in the presence of at least one solvent, with said solvent being water by itself or in a mixture with at least one other solvent, under a reducing atmosphere, and at a temperature of between 50° C. and 300° C., and at a pressure of between 0.5 MPa and 20 MPa, in which
said homogeneous catalyst(s) is/are selected from among inorganic Brønsted acids and organic Brønsted acids
said heterogeneous catalyst(s) is/are selected from among heterogeneous catalyst(s) comprising: at least one metal that is selected from among the metals of groups 6 to 11 and the metals of group 14 of the periodic table; and a substrate that is selected from among perovskites of formula ABO 3 , in which A is selected from among elements Mg, Ca, Sr and Ba, and La, and B is selected from among: elements Fe, Mn, Ti, and Zr; oxides of elements selected from among lanthanum (La), neodymium (Nd) and yttrium (Y), cerium (Ce) and niobium (Nb), by themselves or in a mixture; and mixed oxides that are selected from among aluminates of zinc (Zn), copper (Cu), and cobalt (Co), by themselves or in a mixture.

2. The process according to claim 1 , in which said feedstock is brought into contact simultaneously with a catalytic system that consists of said homogeneous catalyst(s) and said heterogeneous catalyst(s).

3. The process according to claim 1 , in which the homogeneous catalyst(s) is/are selected from among the inorganic Brønsted acids, which are selected from among the following inorganic acids: HF, HCl, HBr, HI, H 2 SO 3 , H 2 SO 4 , H 3 PO 2 , H 3 PO 4 , HNO 2 , HNO 3 , H 2 WO 4 , H 4 SiW 12 O 40 , H 3 PW 12 O 40 , (NH 4 ) 6 (W 12 O 40 ).xH 2 O, H 4 SiMo 12 O 40 , H 3 PMo 12 O 40 , (NH 4 ) 6 Mo 7 O 24 .xH 2 O, H 2 MoO 4 , HReO 4 , H 2 CrO 4 , H 2 SnO 3 , H 4 SiO 4 , H 3 BO 3 , HClO 4 , HBF 4 , HSbF 5 , HPF 6 , H 2 FO 3 P, C1SO 3 H, FSO 3 H, HN(SO 2 F) 2 and HIO 3 .

4. The process according to claim 3 , in which the inorganic Brønsted acids are selected from among the following inorganic acids: HCl, H 2 SO 4 , H 3 PO 4 , H 2 WO 4 , H 2 MoO 4 , HReO 4 , and H 2 CrO 4 .

5. The process according to claim 4 , in which the inorganic Brønsted acid is tungstic acid H 2 WO 4 .

6. The process according to claim 1 , in which the homogeneous catalyst(s) is/are selected from among the organic Brønsted acids, which are selected from among organic acids of the formulas R—COOH, RSO 2 H, RSO 3 H, (RSO 2 )NH, (RO) 2 PO 2 H, and ROH where R is a hydrogen or a carbon-containing chain that consists of alkyl or aryl groups, substituted or not by heteroatoms.

7. The process according to claim 6 , in which the organic Brønsted acids are selected from among formic acid, acetic acid, trifluoroacetic acid, lactic acid, levulinic acid, methanesulfinic acid, methanesulfonic acid, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)amine, benzoic acid, paratoluenesulfonic acid, 4-biphenylsulfonic acid, diphenyl phosphate, and 1,1′-binaphthyl-2,2′-diyl hydrogenophosphate.

8. The process according to claim 7 , in which the organic Brønsted acid is selected from among methanesulfonic acid and acetic acid.

9. The process according to claim 1 , in which the metal of the heterogeneous catalyst or catalysts is selected from among the metals Mo, W, Re, Ru, Co, Rh, Jr, Ni, Pd, Pt, Cu and Sn, taken by themselves and in a mixture.

10. The process according to claim 9 , in which the metal of the heterogeneous catalyst or catalysts is selected from among the metals Ni, Pt, Ru and Sn, taken by themselves or in a mixture.

11. The process according to claim 1 , in which the homogeneous catalysts are introduced into the reaction chamber at a rate of a quantity that corresponds to a feedstock/homogeneous catalyst(s) ratio by mass of between 1.5 and 1,000.

12. The process according to claim 1 , in which the solvent is water only.

13. The process according to claim 1 , in which the reducing atmosphere is a hydrogen atmosphere, pure or in a mixture.

14. The process according to claim 1 , operating at a temperature of between 80° C. and 250° C., and at a pressure of between 2 MPa and 20 MPa.

Assignees

• Ifp Energies Now

Inventors

• Girard Etienne
• Cabiac Amandine
• Delcroix Damien

Classifications

• B01J23/78

  with alkali- or alkaline earth metals · CPC title

• B01J23/8906

  Iron and noble metals · CPC title

• B01J23/755

  Nickel · CPC title

• B01J23/34

  Manganese · CPC title

• C07C31/20

  Dihydroxylic alcohols · CPC title