Catalyst for producing aliphatic ketones from fermented product of biomass, and method for producing same

Patent metadata

Field	Value
Publication number	US-11235311-B2
Application number	US-201816477419-A
Country	US
Kind code	B2
Filing date	Jan 9, 2018
Priority date	Jan 11, 2017
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

The present disclosure discloses: a bifunctional Cu/Ce—Zr-based catalyst suitable for reacting a ketone and alcohol which are contained in a fermented product of biomass and have a low molecular weight, and converting same into an aliphatic ketone having an increased carbon number; a method for producing the catalyst; and a method for producing a fuel-range aliphatic ketone, such as gasoline and air fuel, by using the catalyst.

First claim

The invention claimed is:

1. A method of producing a Cu/Ce—Zr-based catalyst for aldol condensation, the method comprising:
a) preparing a mixed support represented by a general formula Ce x Zr 1-x O 2 (x is 0.5-0.95);
b) loading a Cu 2+ precursor on the mixed support;
c) converting the Cu 2+ precursor-loaded mixed support into its oxide form via calcination, and
d) reducing the oxide obtained in step c) to produce a catalyst represented by Cu/Ce x Zr 1-x O 2 , whereby CuO in the oxide is converted into its reduced form (Cu 0 ),
wherein (i) the Cu content is 0.5 to 20 wt % on the element basis, (ii) the oxygen storage capacity is 500 to 1000 μmol/g, (iii) the specific Cu surface area is 1 to 60 m 2 /g, and (iv) the amount of CO 2 -TPD in the Cu/Ce x Zr 1-x O 2 catalyst is in a range of 100 to 600 μmol/g.

2. The method of claim 1 , wherein the specific (BET) surface area of the mixed support prepared in step a) is at least 90 m 2 /g and the specific (BET) surface area of the oxide prepared in step c) is at least 70 m 2 /g.

3. The method of claim 1 , wherein the Cu 2+ precursor, as a water-soluble copper salt, is copper nitrate, copper sulfate, copper acetate, copper formate, copper (II) chloride, copper iodide, or a combination thereof.

4. The method of claim 1 , wherein step a) comprises:
a1) preparing precursor solutions for a support, the precursor solutions containing a Ce precursor and a Zr precursor;
a2) forming a Ce—Zr composite precursor from the precursor solutions for a support; and
a3) calcining the Ce—Zr composite precursor to form a mixed support in an oxide form.

5. The method of claim 4 , wherein each of the Ce precursor and the Zr precursor is in the form of water-soluble metal salt.

6. The method of claim 5 , wherein each of the Ce precursor and the Zr precursor is in the form of halide, hydroxide, nitrate, sulfate, oxalate, carbonate, acetate, ammonium nitrate salt, phosphate, a compound containing oxide of its corresponding metal element, or a combination thereof.

7. The method of claim 4 , wherein step a2) is performed by coprecipitation.

8. The method of claim 1 , wherein step b) is performed by impregnation, deposition, ion-exchange, or deposition-precipitation.

9. The method of claim 1 , wherein step c) is performed under a temperature of 300 to 500° C. and an oxygen atmosphere for 2 to 10 hours.

10. The method of claim 1 , wherein step d) is performed at a temperature of 180 to 320° C. using a reducing gas containing hydrogen and/or carbon monoxide, which optionally contains an inert gas.

11. A Cu/Ce—Zr-based catalyst for aldol condensation in which Cu particles or clusters are supported on a mixed support represented by Ce x Zr 1-x O 2 (x is 0.5-0.95), the Cu particles or clusters being a reduced form thereof (Cu 0 ),
wherein (i) the Cu content is 0.5 to 20 wt % on the element basis, (ii) the oxygen storage capacity is 500 to 1000 μmol/g, (iii) the specific Cu surface area is 1 to 60 m 2 /g, and (iv) the amount of CO 2 -TPD in the Cu/Ce x Zr 1-x O 2 , catalyst is in a range of 100 to 600 μmol/g.

12. The catalyst of claim 11 , wherein the catalyst has a form in which Cu particles or clusters are dispersed on the Ce x Zr 1-x O 2 mixed support and the size of the Cu particles or clusters is in a range of 5 to 100 nm.

13. A method for producing aliphatic ketones from a fermented product of biomass, the method comprising:
A) obtaining a fermented product of biomass containing acetone and butanol;
B) converting a reactant derived from the fermented product of biomass into aliphatic ketones via a condensation reaction using a Cu/Ce—Zr-based catalyst; and
C) separating and recovering the aliphatic ketones from the reaction product,
wherein in the Cu/Ce—Zr-based catalyst, Cu particles or clusters are supported on a mixed support represented by Ce x Zr 1-x O 2 (x is 0.5-0.95), the Cu particles or clusters are the reduced form thereof (Cu 0 ), and the Cu/Ce—Zr-based catalyst satisfies the following requirements (i) to (iv):
wherein (i) the Cu content is 0.5 to 20 wt % on the element basis, (ii) the oxygen storage capacity is 500 to 1000 μmol/g, (iii) the specific Cu surface area is 1 to 60 m 2 /g, and (iv) the amount of CO 2 -TPD in the Cu/Ce x Zr 1-x O 2 , catalyst is in a range of 100 to 600 μmol/g.

14. The method of claim 13 , further comprising, separating a reactant including acetone and butanol from the fermented product of biomass, wherein the separated reactant is provided as the reactant derived from the fermented product of biomass in step B).

15. The method of claim 14 , wherein the molar ratio of acetone:butanol in the separated reactant is in a range of 0.1 to 2:1.

16. The method of claim 13 , further comprising, separating a reactant including acetone, butanol, and ethanol from the fermented product of biomass, wherein the separated reactant is provided as the reactant derived from the fermented product of biomass in step B).

17. The method of claim 13 , wherein step B) is performed under conditions of a temperature of 160 to 300° C. and a pressure of 1 to 100 bar.

18. The method of claim 13 , wherein the aliphatic ketones have 6 to 14 carbon atoms.

Assignees

• Univ Hanyang Ind Univ Coop Found

Inventors

• Suh Young Woong
• Kim Min Seok
• Park Jong Ha

Classifications

• Y02E50/10

  Biofuels, e.g. bio-diesel · CPC title

• C12P7/36

  produced from substrate containing grain or cereal material · CPC title

• C12P7/28

  Acetone-containing products · CPC title

• C12P7/16

  Butanols · CPC title

• B01J37/0207

  Pretreatment of the support · CPC title