Monolithic catalyst used for carbon dioxide hydrogenation reaction and method for preparing same

Patent metadata

Field	Value
Publication number	US-11338273-B2
Application number	US-201716087341-A
Country	US
Kind code	B2
Filing date	Mar 21, 2017
Priority date	Mar 21, 2016
Publication date	May 24, 2022
Grant date	May 24, 2022

Abstract

A monolithic catalyst used for a carbon dioxide hydrogenation reaction and a method for preparing the same. The catalyst comprises a carrier, a coating, and active components. The carrier is a honeycomb ceramic. The coating and the active components are separately applied to honeycomb ceramic hole walls from inside to outside. Moreover, each of the honeycomb ceramic holes is divided into an upper segment and a lower segment, and different active components are separately loaded on the two segments. The method for preparing the monolithic catalyst comprises first applying a coating to a honeycomb ceramic by means of impregnation to obtain a coating-containing carrier, and then applying active components to an upper segment and a lower segment of the coating-containing carrier successively by means of impregnation to obtain the monolithic catalyst.

First claim

The invention claimed is:

1. A monolithic catalyst, comprising: a carrier, a coating, a first active component deposited on the coating, and a second active component deposited on the coating, said carrier being a honeycomb ceramic carrier comprising a plurality of holes that extend through the honeycomb ceramic carrier, wherein the coating is applied to a wall of each of the plurality of holes, the honeycomb ceramic carrier is divided into an upper segment and a lower segment in a longitudinal direction, wherein a length of the lower segment is from about ¼ to about ⅘ of a total length of the honeycomb ceramic carrier,
wherein the first active component comprises oxides of zinc, aluminum, and optionally copper, and is deposited on the coating on the wall in each hole in the upper segment, and the second active component comprises one or more among bimetallic oxide of Cu—Zn, bimetallic oxide of Ni—Al, polymetallic oxide of Cu—Zn—Zr, and polymetallic oxide Cu—Zn—Al—Zr—Co, and is deposited on the coating on the wall in each hole in the lower segment.

2. The monolithic catalyst according to claim 1 is effective in catalyzing a CO 2 hydrogenation reaction.

3. The monolithic catalyst according to claim 1 is effective in catalyzing a CO 2 -rich syngas hydrogenation reaction.

4. The monolithic catalyst according to claim 1 , wherein the honeycomb ceramic is a cylindrical cordierite having a cross-sectional diameter equal to an inner diameter of a hydrogenation tubular reactor, and a ratio of the length of the honeycomb ceramic to the cross-sectional diameter thereof is from about 1.5 to about 6:1.

5. The monolithic catalyst according to claim 1 , wherein the honeycomb ceramic is a cylindrical cordierite, each hole has a cross-sectional shape that is a circle or a square, and a diameter of the circle or a length of a side of the square is from about 1 mm to about 5 mm.

6. The monolithic catalyst according to claim 1 , wherein the length of the lower segment is from about ½ to about ¾ of the total length of the honeycomb ceramic carrier.

7. The monolithic catalyst according to claim 1 , wherein the coating is Al 2 O 3 or γ-Al 2 O 3 .

8. The monolithic catalyst according to claim 1 , wherein the first active component comprises bimetallic oxide of Zn—Al, polymetallic oxide of Cu—Zn—Al, or both.

9. The monolithic catalyst according to claim 2 , wherein the first active component comprises zinc and aluminum, and a molar ratio of zinc to aluminum is (about 0.4-about 0.6):1, and the second active component comprises copper, zinc, aluminum, zirconium, and cobalt, and a molar ratio of copper, zinc, aluminum, zirconium, and cobalt is 1:(about 0.8-about 1.2):(about 0.5-about 1):(about 0.5-about 1.5)):(about 0.1-about 0.8).

10. The monolithic catalyst according to claim 2 , wherein the first active component comprises zinc and aluminum, and a molar ratio of zinc to aluminum is (about 0.4-about 0.6):1, and the second active component comprises copper and zinc, and a molar ratio of copper to zinc is (about 0.1-about 0.5):1.

11. The monolithic catalyst according to claim 2 , wherein the first active component comprises zinc and aluminum, and a molar ratio of zinc to aluminum is (about 0.4-about 0.6):1, and the second active component comprises nickel and aluminum, and a molar ratio of nickel to aluminum is (about 0.1-about 0.5):1.

12. The monolithic catalyst according to claim 3 , wherein the first active component comprises copper, zinc, and aluminum, and a molar ratio of copper, zinc, and aluminum is 100:(about 30-about 120):(about 10-about 50), and the second active component comprises copper, zinc, and zirconium, and a molar ratio of copper, zinc, and zirconium is 100:(about 30-about 120):(about 20-about 100).

13. The monolithic catalyst according to claim 1 , wherein the catalyst is placed in a single reactor that is adiabatic or non-adiabatic.

14. A process for preparation of the monolithic catalyst according to claim 1 , comprising:
a. immersing the honeycomb ceramic carrier in a mixed aqueous solution of aluminum nitrate and urea for treatment to obtain a precursor of a coating-containing carrier, and heat-treating the precursor to obtain a coated carrier;
b. impregnating the upper segment of the coated carrier in solution A, or impregnating the lower segment of the coated carrier in solution B, then contacting the impregnated segment with a first precipitant solution, then after washing, obtaining a catalyst precursor 1 , and heat-treating the catalyst precursor 1 to obtain a first catalyst semi-finished product having an untreated lower segment or a second catalyst semi-finished product having an untreated upper segment; and
c. impregnating the untreated lower segment of the first catalyst semi-finished product in solution B, or impregnating the untreated upper segment of the second catalyst semi-finished product resultant in solution A, then contacting the impregnated lower segment of the first catalyst semi-finished product or the impregnated upper segment of the second catalyst semi-finished product with a second precipitant solution, then after washing, obtaining a catalyst precursor 2 , and heat-treating the catalyst precursor 2 to obtain the monolithic catalyst.

15. The process according to claim 14 , wherein the impregnation in the preparation step a is carried out in an autoclave at a pressure of from about 0.5 MPa to about 6 MPa, at a temperature of from about 70° C. to about 150° C., for a period of from about 1 h to about 5 h.

16. The process according to claim 14 , wherein the heat treatment in the preparation step a comprises firstly drying at about 120° C. for about 4 h, and then calcining at about 600 to about 800° C. for from about 1 h to about 4 h.

17. The process according to claim 14 , wherein the solution A is a mixed nitrate solution containing zinc and aluminum, or a mixed nitrate solution containing copper, zinc and aluminum, and the solution B is a mixed nitrate solution containing copper, zinc, aluminum, zirconium, and cobalt, a mixed nitrate solution containing copper and zinc, a mixed nitrate solution containing nickel and aluminum, or a mixed nitrate solution containing copper, zinc and zirconium.

18. The process according to claim 14 , wherein the solution A is a mixed nitrate solution containing zinc and aluminum, a pH of the solution A is about 6.0 to about 7.0, a molar ratio of zinc to aluminum is (about 0.4-about 0.6):1, and a total salt molar concentration is from about 0.5 mol/L to about 2 mol/L; and
the solution B is a mixed nitrate solution containing copper, zinc, aluminum, zirconium and cobalt, a pH of the solution B is about 6.0 to about 7.0, a molar ratio of nitrates of copper, zinc, aluminum, zirconium and cobalt is 1:(about 0.8-about 1.2):(about 0.5-about 1):(about 0.5-about 1.5):(about 0.1-about 0.8), and a total salt molar concentration is from about 0.5 mol/L to about 1 mol/L.

19. The process according to claim 14 , wherein the solution A is a mixed nitrate solution containing zinc and aluminum, a pH of the solution A is from about 6.0 to about 7.0, and a molar ratio of zinc to aluminum is (about 0.4-about 0.6):1, a total salt molar concentration is from about 0.5 mol/L to about 2 mol/L; and
the solution B is a mixed nitrate solution containing copper and zinc, a pH of the solution B is from about 6.0 to about 7.0, a molar ratio of copper to zinc is (about 0.1-about 0.5):1, and a total salt molar concentration is from about 0.5 mol/L to about 1 mol/L.

20. The process according to clai

Assignees

• China Petroleum & Chem Corp
• Sinopec Nanjing Res Institute Of Chemical Industry Co Ltd

Inventors

• Yu Yang
• Chen Haibo
• Wei Shixin
• Yin Yusheng
• Mao Chunpeng
• Tan Jiedong
• Qiu Dong
• Xie Tianming
• He Jian
• Yin Huiqin
• Tian Xianguo
• Dong Tianlei
• Wang Qiong

Classifications

• B01J35/57

  Honeycombs · CPC title

• B01J23/80 Primary

  with zinc, cadmium or mercury · CPC title

• B01J23/002 Primary

  Mixed oxides other than spinels, e.g. perovskite · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• C07C29/153

  characterised by the catalyst used · CPC title