Zirconium-based metal-organic frameworks as catalyst for transfer hydrogenation

Patent metadata

Field	Value
Publication number	US-10195592-B2
Application number	US-201715584933-A
Country	US
Kind code	B2
Filing date	May 2, 2017
Priority date	May 3, 2016
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

The present invention relates to a catalyst for transfer hydrogenation, which is formed of a metal-organic framework having an MOF-808 based X-ray diffraction pattern.
A high crystalline porous MOF-808 based metal-organic framework exhibits excellent performance in the transfer hydrogenation of ethyl levulinate (EL) at high and low temperature.

First claim

The invention claimed is:

1. A method of transfer hydrogenation, comprising transferring hydrogen from a hydrogen donor to a hydrogen acceptor by using a catalyst which is formed of a metal-organic framework having an MOF-808 based X-ray diffraction pattern.

2. The method of claim 1 , wherein the metal-organic framework is represented by Formula 1 or Formula 2 below:
M 6 O 4 (OH) 4 (BTC) 2 (HCOO) 6   [Formula 1]

wherein M is a group 4A or 4B element, or a lanthanide metal whose oxidation state is 4 + ,and BTC is Benzenetricarboxylate:
M 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6 -x(H 2 O) 6 (BTC) 2 (HCOO) x   [Formula 2]

wherein x is any number in the range of 0to 6, M is a group 4A or 4B element, or a lanthanide metal whose oxidation state is 4 + , and BTC is Benzenetricarboxylate.

3. The method of claim 1 , wherein the transfer hydrogenation is the transfer hydrogenation of ethyl levulinate (EL) into γ-valerolactone.

4. The method of claim 2 , wherein the transfer hydrogenation is the transfer hydrogenation of ethyl levulinate (EL) into γ-valerolactone.

5. The method of claim 1 , wherein the transfer hydrogenation is the transfer hydrogenation of furfural to furfuryl alcohol; levulinic acid (LA) to γ-valerolactone (GVL); furfural to 2-methylfuran (2-MF); 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); glycerol to 1,2-propanediol (1,2-PDO); fructose to 5-hydroxymethylfurfural (HMF); glucose to γ-valerolactone (GVL); fructose to γ-valerolactone (GVL); butyl levulinate (BL) to γ-valerolactone (GVL); glycerol to 1,2-PDO; (1-hydroxyethyl)benzene (1-HB) to ethylbenzene; 5-hydroxymethylfurfural (HMF) to 1,6-hexanediol (HDL); benzaldehyde to benzyl alcohol; hexahydrobenzaldehyde to hexahydrobenzyl alcohol; 4-methylbenzaldehyde to 4-methylbenzyl alcohol; methyl phenyl ketone to 1-phenylethanol; hexanal to 1-hexanol; 4-methyl-2-pentanone to 4-methyl-2-pentanol; cinnamaldehyde to cinnamyl alcohol; thiophene-2-aldehyde to 2-(hydroxymethyl) thiophene; 4-pyridinecarboxaldehyde to 4-pyridylcarbinol; or giranial to geraniol.

6. The method of claim 2 , wherein the transfer hydrogenation is the transfer hydrogenation of furfural to furfuryl alcohol; levulinic acid (LA) to γ-valerolactone (GVL); furfural to 2-methylfuran (2-MF); 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF); glycerol to 1,2-propanediol (1,2-PDO); fructose to 5-hydroxymethylfurfural (HMF); glucose to γ-valerolactone (GVL); fructose to γ-valerolactone (GVL); butyl levulinate (BL) to γ-valerolactone (GVL); glycerol to 1,2-PDO; (1-hydroxyethyl)benzene (1-HB) to ethylbenzene; 5-hydroxymethylfurfural (HMF) to 1,6-hexanediol (HDL); benzaldehyde to benzyl alcohol; hexahydrobenzaldehyde to hexahydrobenzyl alcohol; 4-methylbenzaldehyde to 4-methylbenzyl alcohol; methyl phenyl ketone to 1-phenylethanol; hexanal to 1-hexanol; 4-methyl-2-pentanone to 4-methyl-2-pentanol; cinnamaldehyde to cinnamyl alcohol; thiophene-2-aldehyde to 2-(hydroxymethyl) thiophene; 4-pyridinecarboxaldehyde to 4-pyridylcarbinol; or giranial to geraniol.

7. The method of claim 1 , wherein isopropanol, methanol, ethanol, glycerol, butanol, cyclic ethers, benzyl alcohol, cyclohexanone, 2-propanol, ethylene glycol, 2,3-dihydroindole, 1,2,3,4-tetrahydroquinoline, cyclohexene, cyclohexadiene, limonene, hydrazine, ammonium formate, ammonium hypophosphite, or a mixture thereof is used as the hydrogen donor.

8. The method of claim 2 , wherein isopropanol, methanol, ethanol, glycerol, butanol, cyclic ethers, benzyl alcohol, cyclohexanone, 2-propanol, ethylene glycol, 2,3-dihydroindole, 1,2,3,4-tetrahydroquinoline, cyclohexene, cyclohexadiene, limonene, hydrazine, ammonium formate, ammonium hypophosphite, or a mixture thereof is used as the hydrogen donor.

9. The method of claim 1 , wherein the transfer hydrogenation is performed at a low temperature of 200° C. or below by using the catalyst.

10. The method of claim 2 , wherein the transfer hydrogenation is performed at a low temperature of 200° C. or below by using the catalyst.

11. The method of claim 1 , wherein the transfer hydrogenation is the open-system transfer hydrogenation which utilizes a solvent-reflux method.

12. The method of claim 2 , wherein the transfer hydrogenation is the open-system transfer hydrogenation which utilizes a solvent-reflux method.

13. A method of preparing γ-valerolactone by transfer hydrogenation of ethyl levulinate (EL) using a catalyst which is formed of a metal-organic framework having an MOF-808 based X-ray diffraction pattern.

14. The method of claim 13 , wherein the metal-organic framework is represented by Formula 1 or Formula 2 below:
M 6 O 4 (OH) 4 (BTC) 2 (HCOO) 6   [Formula 1]

wherein M is a group 4A or 4B element, or a lanthanide metal whose oxidation state is 4 + , and BTC is Benzenetricarboxylate;
M 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6-x (H 2 O) 6 (BTC) 2 (HCOO) x   [Formula 2]

wherein x is any number in the range of 0 to 6, M is a group 4 A or 4 B element, or a lanthanide metal whose oxidation state is 4 + , and BTC is Benzenetricarboxylate.

15. The method of claim 13 , wherein the transfer hydrogenation is performed using isopropanol, methanol, ethanol, glycerol, butanol, cyclic ethers, benzyl alcohol, cyclohexanone, 2-propanol, ethylene glycol, 2,3-dihydroindole, 1,2,3,4 -tetrahydroquinoline, cyclohexene, cyclohexadiene, limonene, hydrazine, ammonium formate, ammonium hypophosphite, or a mixture thereof as a hydrogen donor.

16. The method of claim 14 , wherein the transfer hydrogenation is performed using isopropanol, methanol, ethanol, glycerol, butanol, cyclic ethers, benzyl alcohol, cyclohexanone, 2-propanol, ethylene glycol, 2,3-dihydroindole, 1,2,3,4-tetrahydroquinoline, cyclohexene, cyclohexadiene, limonene, hydrazine, ammonium formate, ammonium hypophosphite, or a mixture thereof as a hydrogen donor.

17. The method of claim 13 , wherein the transfer hydrogenation is performed in a non-homogenous catalytic system.

18. The method of claim 13 , wherein the transfer hydrogenation of ethyl levulinate (EL) is performed in an open-system which utilizes a non-homogenous catalyst and a solvent-reflux method.

19. A method for preparing furfuryl alcohol by transfer hydrogenation of furfural using a catalyst which is formed of a metal-organic framework having an MOF-808 based X-ray diffraction pattern.

20. The method of claim 19 , wherein the metal-organic framework is represented by Formula 1 or Formula 2 below:
M 6 O 4 (OH) 4 (BTC) 2 (HCOO) 6   [Formula 1]

wherein M is a group 4 A or 4 B element, or a lanthanide metal whose oxidation state is 4 + , and BTC is Benzenetricarboxylate;
M 6 (μ 3 -O) 4 (μ 3 -OH) 4 (OH) 6-x (H 2 O) 6 (BTC) 2 (HCOO) x   [Formula 2]

wherein x is any number in the range of 0 to 6 , M is a group 4 A or 4 B element, or a lanthanide metal whose oxidation state is 4 + , and BTC is Benzenetricarboxylate.

Assignees

• Korea Res Inst Chemical Tech

Inventors

• Hwang Young Kyu
• Chang Jong San
• Hong Do Young
• Hwang Dong Won
• Lee U Hwang
• Cho Kyung Ho
• Valekar Anil Haribhau
• Lee Su Kyung

Classifications

• B01J31/26

  containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 · CPC title

• B01J35/1028

  Operations & Transport · mapped topic

• B01J35/1023

  Operations & Transport · mapped topic

• B01J35/1047

  Operations & Transport · mapped topic

• B01J27/20 Primary

  Carbon compounds · CPC title