Selective nickel based hydrogenation catalyst and the preparation thereof

Patent metadata

Field	Value
Publication number	US-9597668-B2
Application number	US-201414456858-A
Country	US
Kind code	B2
Filing date	Aug 11, 2014
Priority date	Nov 1, 2007
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

Abstract

A selective nickel-based hydrogenation catalyst and the preparation thereof, characterized in that: provided that the catalyst is weighed 100%, it comprises nickel oxide 14-20% as active component, lanthanum oxide and/or cerium oxide 2-8%, and VIB element oxide 1-8% as aids, 2-8% silica, 1-8% alkaline earth metal oxides, and alumina as the balance. The catalyst specific surface area is 60-150 m 2 /g, and the pore volume is 0.4-0.6 ml/g. The catalyst has good hydrogenation performance, especially impurity and colloid resistance and hydrogenation stability. The catalyst can be applied to the diolefin selective hydrogenation of medium or low-distillate oil, especially of the full-distillates pyrolysis gasoline.

First claim

What is claimed is:

1. A method for preparing a selective nickel-based hydrogenation catalyst, the method comprising:
adding silica or its precursor and alkaline earth metal oxide or its precursor into an alumina carrier so as to form a first mixture;
calcinating the first mixture at the temperature of 800-1100° C. for 3-6 hours to form a modified alumina carrier;
adding soluble salts of nickel, rare earth element and VIB group element into water so as to form a solution;
adjusting the pH of the solution to 4-5 following full dissolution of the soluble salts to form an impregnating solution;
impregnating the modified alumina carrier with the impregnating solution to form a second mixture;
after impregnating, drying the second mixture at the temperature of 40-120° C.; and
after drying, calcinating the second mixture at the temperature of 350-450° C. for 3-6 hours, thereby obtaining the resultant catalyst,
wherein the modified alumina carrier is prepared by:
adding silica sol, nitric acid and water into alumina hydrate so as to form a third mixture;
after kneading and extruding the third mixture, drying the third mixture at the temperature of 40-120° C.;
after drying, calcinating the third mixture at the temperature of 300-600° C. for 4-6 hours so as to form a carrier;
impregnating the carrier with an impregnating solution formed by adding alkaline earth metal oxide into water;
after impregnating, drying the carrier at the temperature of 40-120° C.; and
after drying, calcinating the carrier at the temperature of 800-1100° C. for 4-6 hours, thereby forming the modified alumina carrier.

2. The method according to claim 1 , wherein the catalyst comprises a nickel oxide in the amount of 15-19%.

3. The method according to claim 1 , wherein the catalyst comprises a lanthanum oxide and/or cerium oxide in the amount of 3-5%.

4. The method according to claim 1 , wherein the catalyst comprises an alkaline earth metal selected from the group consisting of magnesium, strontium, and a mixture thereof.

5. The method according to claim 1 , wherein the catalyst comprises an alkaline earth metal oxide in the amount of 2-5%.

6. The method according to claim 1 , wherein said VIB group element is one or more selected from the group consisting of chromium, molybdenum and tungsten.

7. The method according to claim 1 , wherein the VIB group element oxide in the catalyst is in the amount of 3-6%.

8. A method for preparing a selective nickel-based hydrogenation catalyst, the method comprising:
adding silica or its precursor and alkaline earth metal oxide or its precursor into an alumina carrier so as to form a first mixture;
calcinating the first mixture at the temperature of 800-1100° C. for 3-6 hours to form a modified alumina carrier;
adding soluble salts of nickel, rare earth element and VIB group element into water so as to form a solution;
adjusting the pH of the solution to 4-5 following full dissolution of the soluble salts to form an impregnating solution;
impregnating the modified alumina carrier with the impregnating solution to form a second mixture;
after impregnating, drying the second mixture at the temperature of 40-120° C.; and
after drying, calcinating the second mixture at the temperature of 350-450° C. for 3-6 hours, thereby obtaining the resultant catalyst,
wherein the resultant catalyst comprise alumina as a carrier, wherein based on the total weight of the catalyst, the catalyst comprises:
14-20% nickel oxide as an active component;
1-8% lanthanum oxide and/or cerium oxide;
1-8% VIB group element oxide as aids;
2-8% silica; and
1-8% alkaline earth metal oxide;

wherein said catalyst has a specific surface area of 60-150 m 2 /g and a pore volume of 0.4-0.6 ml/g, and
wherein the modified alumina carrier is prepared by:
adding silica sol, nitric acid and water into alumina hydrate so as to form a third mixture;
after kneading and extruding the third mixture, drying the third mixture at the temperature of 40-120° C.;
after drying, calcinating the third mixture at the temperature of 300-600° C. for 4-6 hours so as to form a carrier;
impregnating the carrier with an impregnating solution formed by adding alkaline earth metal oxide into water;
after impregnating, drying the carrier at the temperature of 40-120° C.; and

after drying, calcinating the carrier at the temperature of 800-1100° C. for 4-6 hours, thereby forming the modified alumina carrier.

9. The method according to claim 8 , wherein the nickel oxide in the catalyst is in the amount of 15-19%.

10. The method according to claim 8 , wherein the lanthanum oxide and/or cerium oxide in the catalyst is in the amount of 3-5%.

11. The method according to claim 8 , wherein said alkaline earth metal is magnesium and/or strontium.

12. The method according to claim 8 , wherein the alkaline earth metal oxide in the catalyst is in the amount of 2-5%.

13. The method according to claim 8 , wherein said VIB group element is one or more selected from the group consisting of chromium, molybdenum and tungsten.

14. The method according to claim 8 , wherein the VIE group element oxide in the catalyst is in the amount of 3-6%.

Assignees

• Petrochina Co Ltd

Inventors

• Liang Shunqin
• Qian Ying
• Lv Longgang
• Sun Limin
• Zheng Yundi
• Wang Tinghai
• Wu Jie
• Cao Fengxia

Classifications

• B01J35/1038

  Operations & Transport · mapped topic

• B01J23/83 Primary

  with rare earths or actinides · CPC title

• B01J21/12

  Silica and alumina · CPC title

• B01J23/866

  Nickel and chromium · CPC title

• B01J37/024

  Multiple impregnation or coating · CPC title