Method for preparing p-hydroxycinnamate by using ionic liquid for catalytic lignin depolymerization

Patent metadata

Field	Value
Publication number	US-10807940-B2
Application number	US-201716642959-A
Country	US
Kind code	B2
Filing date	Nov 21, 2017
Priority date	Aug 31, 2017
Publication date	Oct 20, 2020
Grant date	Oct 20, 2020

Abstract

The present invention discloses a method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization comprising: 1) preparation of a halogen metal-based ionic liquid: preparing the halogen metal-based ionic liquid by reacting an alkylimidazole chloride with a metal chloride by heating the same to 30° C. to 80° C. with stirring; and 2) catalytic depolymerization of lignin: mixing the halogen metal-based ionic liquid and lignin with an alcohol, and after N2 replacement, heating the solution to 140° C. to 200° C. and reacting the solution for 4-8 h while stirring to prepare high value-added chemicals with p-hydroxycinnamate as a main product. The present invention has advantages of a simple process, mild conditions, environmental kindness, and high selectivity for a main product. The ionic liquid is simple in preparation, has a good atom economy, and is recyclable. Under optimal conditions, the yield of p-hydroxycinnamate can reach 40-80 mg/g.

First claim

The invention claimed is:

1. A method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization, wherein the method comprises:
preparation of an ionic liquid: preparing a halogen metal-based ionic liquid by mixing an alkylimidazole chloride with a metal halide at a molar ratio of 1:1 to 2:1 at 30° C. to 80° C. and then extracting and drying; and
depolymerization of lignin: mixing the halogen metal-based ionic liquid and an organosolv lignin, adding a solvent thereto, and after N 2 replacement, heating the solution to 140° C. to 200° C. and reacting the solution for 4-8 h while stirring, filtering and extracting the reaction solution to obtain a biochemical, and concentrating and separating the biochemical to obtain p-hydroxycinnamate.

2. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 1 , wherein the metal halide is aluminum chloride, ferric chloride, chromium chloride, manganese chloride, cobalt chloride, nickel chloride, copper chloride or zinc chloride.

3. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 1 , wherein the cation of the halogen metal-based ionic liquid is an alkylimidazole, and the anion is [FeCl 4 ] − , [CrCl 4 ] − , [AlCl 4 ] − , [MnCl 4 ] 2− , [CoCl 4 ] 2− , [NiCl 4 ] 2− , [CuCl 4 ] 2− or [ZnCl 4 ] 2− .

4. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 1 , wherein the structural formula of the halogen metal-based ionic liquid is as follows:

5. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 1 , wherein the mixing time at 30° C. to 80° C. is 3-8 h, and an extractant used in the preparation of an ionic liquid is ethyl acetate.

6. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic depolymerization according to claim 1 , wherein the solvent is a C1-C7 fatty alcohol, the stirring speed is 150-600 r/min, and the lignin is an agricultural and forestry herbaceous lignin.

7. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 6 , wherein the agricultural and forestry herbaceous lignin is bagasse, wheat straw, corn stalk, corn cob, rice straw, bamboo or Chinese miscanthus ; during the preparation, the organosolv lignin is extracted by the following method: in mass parts, adding 100 parts of deionized water, 150-250 parts of ethanol, 0.5-1.5 parts of sulfuric acid, and 15-30 parts of agricultural and forestry waste powder to a reactor, reacting at 150° C. to 200° C. for 2-6 h, then filtering and separating, adding deionized water to the liquid phase, and then filtering and separating to obtain a solid that is the organosolv lignin.

8. The method for preparing p-hydroxycinnamate by using an ionic liquid according for catalytic lignin depolymerization according to claim 1 , wherein the step of filtering and extracting the reaction solution to obtain a biochemical comprises: adding deionized water to the reaction solution to precipitate unreacted lignin, filtering, and then drying the filter residue at 60° C. to 80° C.; evaporating the filtrate to dryness, adding water before transferring to a separatory funnel, extracting with ethyl acetate three times, and evaporating the extracted phase to dryness to obtain the biochemicals of p-hydroxycinnamate, ferulate, acid compounds, aldehyde compounds and ester derivatives.

9. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 1 , wherein the alkylimidazole chloride is prepared by: mixing N-methylimidazole and 1-chloroalkane at a molar ratio of (0.1-1):(0.12-1.2), stirring at room temperature for 12-24 h, then raising the temperature to 60° C. to 100° C., and continuing to stir for 24-36 h to obtain a mixed solution; washing the mixed solution with ether, and then drying in vacuum to obtain the alkylimidazole chloride.

10. The method for preparing p-hydroxycinnamate by using an ionic liquid for catalytic lignin depolymerization according to claim 4 , wherein a halogen metal-based ionic liquid [C n mim][MCl 4 ] is prepared by: mixing 2-50 mmol of ferric chloride or aluminum chloride or chromium chloride with an equivalent amount of the alkylimidazole chloride, stirring at 30° C. to 50° C. for 3-6 h, then extracting with 5-15 mL of dichloromethane, evaporating the solvent off the resulting solution, and drying in vacuum at 60° C. to 80° C. for 12-24 h to obtain the halogen metal-based ionic liquid [C n mim][MCl 4 ]; and
a halogen metal-based ionic liquid [C n mim] 2 [MCl 4 ] is prepared as follows: mixing 2-50 mmol of manganese chloride or cobalt chloride or nickel chloride or copper chloride or zinc chloride with alkylimidazole chloride at a molar ratio of 1.2, stirring at 60° C. to 80° C. for 3-6 h, then extracting with 5-15 mL of dichloromethane, evaporating the solvent off the resulting solution, and drying in vacuum at 60° C. to 80° C. for 12-24 h to obtain the halogen metal-based ionic liquid [C n mim] 2 [MCl 4 ].

Assignees

• Univ South China Tech

Inventors

• Li Xuehui
• Li Zhangmin
• Cai Zhenping
• Long Jinxing
• Zhao Weijie
• Ma Hongwei

Classifications

• B01J31/30

  Halides · CPC title

• B01J31/0298

  the ionic liquids being characterised by the counter-anions · CPC title

• B01J31/0284 Primary

  of an aromatic ring, e.g. pyridinium · CPC title

• C07C69/732

  of unsaturated hydroxy carboxylic acids · CPC title

• C07C67/30 Primary

  by modifying the acid moiety of the ester, such modification not being an introduction of an ester group · CPC title