High light received heavy oil catalytic cracking catalyst and preparation method therefor

Patent metadata

Field	Value
Publication number	US-9889439-B2
Application number	US-201214364652-A
Country	US
Kind code	B2
Filing date	Apr 13, 2012
Priority date	Dec 15, 2011
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

The present invention relates to a heavy oil catalytic cracking catalyst having a high yield of light oil and preparation methods thereof. The catalyst comprises 2 to 50% by weight of a magnesium-modified ultra-stable rare earth type Y molecular sieve, 0.5 to 30% by weight of one or more other molecular sieves, 0.5 to 70% by weight of clay, 1.0 to 65% by weight of high-temperature-resistant inorganic oxides, and 0.01 to 12.5% by weight of rare earth oxide. The magnesium-modified ultra-stable rare earth type Y molecular sieve is obtained by the following manner: the raw material, a NaY molecular sieve, is subjected to a rare earth exchange, a dispersing pre-exchange, a magnesium salt exchange modification, an ammonium salt exchange for sodium reduction, a second exchange and a second calcination. The catalyst provided in the present invention is characteristic in its high conversion capacity of heavy oil and a high yield of light oil.

First claim

What is claimed is:

1. A heavy oil catalytic cracking catalyst, characterized in that the catalyst comprises 2% to 50% by weight of a magnesium-modified ultra-stable rare earth type Y molecular sieve, 0.5% to 30% by weight of one or more other molecular sieves, 0.5% to 70% by weight of clay, 1.0% to 65% by weight of high-temperature resistant inorganic oxides, and 0.01% to 12.5% by weight of rare earth oxide,
wherein the magnesium-modified ultra-stable rare earth type Y molecular sieve is a magnesium-modified ultra-stable rare earth type Y molecular sieve having 0.2% to 5% by weight of magnesium oxide, 1% to 20% by weight of rare earth oxide, not more than 1.2% by weight of sodium oxide, a crystallinity of 46% to 63%, and a lattice parameter of 2.454 nm to 2.471 nm;
wherein the magnesium-modified ultra-stable rare earth type Y molecular sieve is prepared by a method comprising:
subjecting a NaY molecular sieve which is used as the raw material to a rare earth exchange and a dispersing pre-exchange, wherein the order of the rare earth exchange and the dispersing pre-exchange is not limited, and wherein the rare earth exchange and the dispersing pre-exchange are consecutively conducted without a calcination process therebetween;
then filtering and washing the molecular sieve slurry and subjecting the molecular sieve slurry to a first calcination to afford a rare earth sodium Y molecular sieve; and
then subjecting the rare earth sodium Y molecular sieve to an ammonium salt exchange for sodium reduction, a magnesium salt exchange modification, and a second calcination, so as to obtain a magnesium-modified ultra-stable rare earth type Y molecular sieve, wherein the addition order of the ammonium salt and the magnesium salt is not limited,
wherein the second calcination is performed after the ammonium salt exchange for sodium reduction, and wherein the magnesium salt exchange modification is performed before, after, or both before and after the second calcination; and

wherein the dispersing pre-exchange refers to a process of adjusting the molecular sieve slurry's concentration to a solid content of 80 to 400 g/L and adding 0.2% to 7% by weight of a dispersing agent to carry out dispersing pre-exchange at an exchange temperature of 0° C. to 100° C. for 0.1 to 1.5 h, the dispersing agent in the dispersing pre-exchange process being selected from one or more of sesbania gum powder, boric acid, urea, ethanol, polyacrylamide, acetic acid, oxalic acid, adipic acid, formic acid, hydrochloric acid, nitric acid, citric acid, salicylic acid, tartaric acid, benzoic acid, and starch; and
wherein no ammonium salt is used in the rare earth exchange or the dispersing pre-exchange.

2. The catalyst according to claim 1 , characterized in that the other molecular sieves are selected from the group consisting of one or more of type Y zeolite, L zeolite, ZSM-5 zeolite, β zeolite, aluminum phosphate zeolite, and a Ω zeolite.

3. The catalyst according to claim 1 , characterized in that the other molecular sieves are one or more of type Y zeolite, ZSM-5 zeolite, HY, USY, REY, REHY, REUSY, H-ZSM-5, and β zeolite.

4. The catalyst according to claim 1 , characterized in that the clay is selected from one or more of kaolin, halloysite, montmorillonite, sepiolite, and perlite.

5. The catalyst according to claim 1 , characterized in that the high-temperature-resistant inorganic oxide is selected from one or more of Al 2 O 3 , SiO 2 , SiO 2 —Al 2 O 3 , and AlPO 4 .

6. The catalyst according to claim 1 , characterized in that the method of preparing the magnesium-modified ultra-stable rare earth type Y molecular sieve further comprises:
preparing the heavy oil catalyst, wherein the magnesium-modified ultra-stable rare earth type Y molecular sieve, one or more other molecular sieves, clay, and a precursor of a high-temperature-resistant inorganic oxide are mixed, homogenized, shaped by spraying, calcinated and washed to obtain the heavy oil cracking catalyst product.

7. The catalyst according to claim 1 , characterized in that during the rare earth exchange, the mass ratio RE 2 O 3 /Y zeolite is 0.005 to 0.25, the exchange temperature is 0° C. to 100° C., the exchange pH is 2.5 to 6.0, and the exchange time is 0.1 to 2 h.

8. The catalyst according to claim 1 , characterized in that during the magnesium salt exchange modification, the amount of magnesium added is 0.2% to 8% by weight, the exchange temperature is 0° C. to 100° C., and the exchange time is 0.3 to 1.5 h.

9. The catalyst according to claim 1 , characterized in that during the rare earth exchange, the mass ratio RE 2 O 3 /Y zeolite is 0.01 to 0.20, the exchange temperature is 60° C. to 95° C., the exchange pH is 3.5 to 5.5, and the exchange time is 0.3 to 1.5 h;
during the dispersing pre-exchange, the amount of the dispersing agent added is 0.2% to 5% by weight, the exchange temperature is 60° C. to 95° C., and the exchange time is 0.1 to 1.5 h; and
during the magnesium salt exchange modification, the amount of magnesium added is 0.2% to 8% by weight, the exchange temperature is 60° C. to 95° C., and the exchange time is 0.3 to 1.5 h.

10. The catalyst according to claim 1 , characterized in that between the rare earth exchange and the dispersing pre-exchange, the molecular sieve slurry is washed and filtered.

11. The catalyst according to claim 6 , characterized in that a tank-type exchange, a belt-type exchange and/or a filter cake exchange is employed for the exchange process of the rare earth exchange or the dispersing pre-exchange.

12. The catalyst according to claim 1 , characterized in that in the rare earth exchange, the rare earth compound solution is divided into multiple portions for multiple exchanges, and each of the multiple exchanges is a tank-type exchange, a belt-type exchange and/or a filter cake exchange.

13. The catalyst according to claim 1 , characterized in that in the dispersing pre-exchange, the dispersing agent is divided into multiple portions for multiple exchanges, and each of the multiple exchanges is a tank-type exchange, a belt-type exchange and/or a filter cake exchange.

14. The catalyst according to claim 1 , characterized in that when the rare earth exchange and the dispersing pre-exchange are carried out alternately multiple times.

15. The catalyst according to claim 1 , characterized in that the calcination condition for the first calcination of the molecular sieve is calcination at 350° C. to 700° C. under 0 to 100% water vapor for 0.3 to 3.5 h.

16. The catalyst according to claim 6 , characterized in that the precursor of the high-temperature-resistant inorganic oxide is selected from the group consisting of silica-alumina gel, silica sol, alumina sol, silica-alumina composite sol, and pseudoboehmite.

17. The catalyst according to claim 13 , characterized in that the rare earth compound is rare earth chloride, rare earth nitrate or rare earth sulfate.

18. The catalyst according to claim 1 , wherein the rare earth is lanthanum-rich rare earth, cerium-rich rare earth, pure lanthanum rare earth or pure cerium rare earth.

19. The catalyst according to claim 1 , characterized in that the magnesium salt is magnesium chloride, magnesium nitrate, or magnesium sulfate.

20. The catalyst according to claim 6 , characterized in that the calcination condition in the step of preparing the heavy oil catalyst is calcinating the sprayed microspheres at 200° C. to 700° C. for 0.05 to 4 hours.

21. The catalyst according to claim 6 , characterized in th

Assignees

• Gao Xionghou
• Zhang Haitao
• Duan Hongchang
• Li Di
• Li Xueli
• Tan Zhengguo
• Huang Xiaoliang
• Cai Jinjun
• Zheng Yunfeng
• Zhang Chenxi
• Cao Gengzhen
• Petrochina Co Ltd

Inventors

• Gao Xionghou
• Zhang Haitao
• Duan Hongchang
• Li Di
• Li Xueli
• Tan Zhengguo
• Huang Xiaoliang
• Cai Jinjun
• Zheng Yunfeng
• Zhang Chenxi
• Cao Gengzhen

Classifications

• B01J2229/186

  not in framework positions · CPC title

• B01J29/088 Primary

  Y-type faujasite · CPC title

• B01J29/84

  Aluminophosphates containing other elements, e.g. metals, boron · CPC title

• B01J2229/42

  Addition of matrix or binder particles · CPC title

• C01B39/24

  Type Y {(C01B39/205 takes precedence)} · CPC title