CO oxidation promoter and a process for the preparation thereof

Patent metadata

Field	Value
Publication number	US-10315186-B2
Application number	US-201514592808-A
Country	US
Kind code	B2
Filing date	Jan 8, 2015
Priority date	Dec 30, 2013
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

The invention relates to a CO oxidation promoter additive and a method of its preparation. The CO oxidation promoter additive is having improved apparent bulk density and attrition properties for use in hydrocarbon conversion during fluid catalytic cracking. The CO oxidation promoter additive has a better CO to CO2 conversion.

First claim

We claim:

1. An additive support for a CO oxidation promoter additive comprising pseudoboehmite alumina having a crystallite size in the range of 10 to 20 Å, a surface area in the range of 200 to 450 m 2 /g, an average pore diameter in the range of 35 to 45 Å, and an average pore volume in the range of 0.2 to 0.6 cm 3 /gm;
wherein the additive support is having self-binding properties and less than 0.2% of residual sodium oxide;
wherein the additive support is prepared by a process comprising: (a) reacting aluminium sulphate with sodium hydroxide by sequential addition of sodium hydroxide solution into solution of aluminium sulphate at a temperature of 25 to 100° C. to obtain a slurry, (b) continuing the reaction until pH of the slurry is reached to 9.5, (c) filtering the slurry to obtain a wet cake, (d) washing the wet cake with hot water, (e) hydrothermal treatment for crystallization of wet cake at a crystallization temperature of 70 to 130° C. for the duration in the range of 12 h-48 h and filter the crystallize material to obtain pseudoboehmite alumina support, (f) preparing a slurry by intimate mixing of pseudoboehmite alumina support and water, (g) peptizing with an organic acid under stirring, and (h) spray drying the slurry of step (g) to obtain microspheres of pseudoboehmite alumina support;
wherein the CO oxidation promoter additive is having an apparent bulk density (ABD) above 0.95 g/cm 3 , and an attrition of less than 5%;
wherein the CO oxidation promoter additive is having conversion efficiency in the range of 85-97 and CO 2 /CO ratio in the range of 20-51.

2. The support of claim 1 having a surface area in the range of 250 to 430 m 2 /gm.

3. The support of claim 1 having an average pore volume in the range of 0.3 to 0.6 cm 3 /gm, and an average pore diameter in the range of 40 to 45 Å.

4. The support of claim 1 having a crystallinity more than 92%, and a crystallite size of 20 Å.

5. A process for preparing the additive support comprising pseudoboehmite alumina of claim 1 , the process comprising:
(a) reacting aluminium sulphate with sodium hydroxide at a temperature of about 25 to about 100° C. to obtain a slurry,
(b) continuing the reaction until pH of the slurry is reached to about 9.5,
(c) filtering the slurry to obtain a wet cake,
(d) washing the wet cake with hot water,
(e) hydrothermal treatment for crystallization of wet cake at a crystallization temperature of about 70 to about 130° C. for the duration of above 12 h-48 h and filter the crystallize material to obtain pseudoboehmite alumina support;
preparing a slurry by intimate mixing of pseudoboehmite alumina support and water,
(g) peptizing with an organic acid under stirring, and
(h) spray drying the slurry of step (g) to obtain microspheres of pseudoboehmite alumina support.

6. The process of claim 5 , wherein the reaction of aluminium sulphate with sodium hydroxide is carried out by sequential addition of sodium hydroxide solution into solution of aluminium sulphate.

7. The process of claim 5 , wherein the reaction of aluminium sulphate with sodium hydroxide is carried out at a temperate of about 35° C. for 0.5 to 5 hours.

8. The process of claim 5 , wherein the concentration of sodium hydroxide is about 3 to about 7 wt %.

9. The process of claim 5 , wherein the washing of wet cake is carried out by hot water at a temperature of 60 to 80° C.

10. The process of claim 5 , wherein crystallization of alumina cake is carried out at a temperature of about 80° C. to about 120° C. for the duration of above 12 h-48 h.

11. The process of claim 5 , wherein the organic acid for peptizing is selected from the group comprising formic acid, acetic acid and mixtures thereof.

12. A process for the preparation of the carbon monoxide (CO) oxidation promoter additive of claim 1 having improved apparent bulk density (ABD) and attrition properties for use in hydrocarbon conversion, comprising the steps of:
(a) preparing a pseudoboehmite alumina support by reacting aluminium sulphate with sodium hydroxide at a temperature ranging from about 25 to about 100° C.;
(b) preparing a slurry by mixing the pseudoboehmite alumina of step (a) with water;
(c) peptizing the slurry prepared in step (b) with an organic acid under stirring;
(d) spray drying the peptized slurry obtained in step (c) to obtain microspheres;
(e) calcining the microspheres of step (d) to obtain calcined microspheres,
(f) impregnating the microspheres of step (e) with a group VIII B metal and drying to obtain CO oxidation promoter.

13. The process of claim 12 , wherein the reaction of aluminium sulphate with sodium hydroxide is carried out by sequential addition of sodium hydroxide solution into solution of aluminium sulphate.

14. The process of claim 12 , wherein the step (a) further comprises, continuing the reaction of aluminium sulphate with sodium hydroxide until pH of the slurry is reached to about 9.5, filtering the slurry to obtain wet cake, and washing the wet cake with hot water to obtain pseudoboehmite alumina support.

15. The process of claim 12 , wherein crystallization of alumina cake is carried out at a temperature of about 80 to about 120° C. for the duration of above 12 h-48 h.

16. The process of claim 12 , wherein the organic acid for peptizing is selected from the group comprising formic acid, acetic acid, and mixtures thereof.

17. The process of claim 12 , wherein the calcining is carried out at a temperature of about 450 to about 650° C.

18. The process of claim 12 , wherein the group VIII B metal is selected from platinum and palladium.

19. The CO oxidation promoter additive of claim 12 having, and an attrition of less than 5%, pore volume 0.2-0.5 cc/gm and average pore diameter in the range of 40-45 Å.

20. A method of promoting CO oxidation during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components said method comprising contacting a hydrocarbon feedstock with a cracking catalyst and the CO oxidation promoter additive of claim 19 , said CO oxidation promoter being present in an amount sufficient to reduce said CO emissions.

21. The method of claim 20 , wherein the additive is mixed with the cracking catalyst at 0.3% concentration having platinum less than 3 ppm in the total catalyst and additive mixture.

22. The method of claim 20 , wherein the catalyst is spent catalyst.

Assignees

• Indian Oil Corp Ltd

Inventors

• LOGANATHAN Kumaresan
• Kuvettu Mohan Prabhu
• Karthikeyani Arumugam Velayutham
• Sarkar Biswanath
• Swamy Balaiah
• PULIKOTTIL Alex
• Kasliwal Pankaj Kumar
• Christopher Jayaraj
• Kumar Brijesh
• Rajagopal Santanam

Classifications

• C10G2300/405

  Limiting CO, NOx or SOx emissions · CPC title

• C10G11/18

  according to the "fluidised-bed" technique · CPC title

• B01J37/06

  Washing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/038 Primary

  to form slurries or suspensions, e.g. a washcoat · CPC title

• B01J37/009

  Preparation by separation, e.g. by filtration, decantation, screening · CPC title