Dual catalyst system for propylene production

Patent metadata

Field	Value
Publication number	US-9884794-B2
Application number	US-201615190981-A
Country	US
Kind code	B2
Filing date	Jun 23, 2016
Priority date	Jul 2, 2015
Publication date	Feb 6, 2018
Grant date	Feb 6, 2018

Abstract

Embodiments of processes for producing propylene utilize a dual catalyst system comprising a mesoporous silica catalyst impregnated with metal oxide and a mordenite framework inverted (MFI) structured silica catalyst downstream of the mesoporous silica catalyst, where the mesoporous silica catalyst includes a pore size distribution of at least 2.5 nm to 40 nm and a total pore volume of at least 0.600 cm 3 /g, and the MFI structured silica catalyst has a total acidity of 0.001 mmol/g to 0.1 mmol/g. The propylene is produced from the butene stream via metathesis by contacting the mesoporous silica catalyst and subsequent cracking by contacting the MFI structured silica catalyst.

First claim

What is claimed is:

1. A process for production of propylene comprising:
providing a dual catalyst system comprising:
a mesoporous silica catalyst impregnated with metal oxide, where the mesoporous silica catalyst includes a pore size distribution of about 2.5 nm to about 40 nm and a total pore volume of at least about 0.600 cm 3 /g, and
a mordenite framework inverted (MFI) structured silica catalyst directly downstream of the mesoporous silica catalyst, where the MFI structured silica catalyst includes a total acidity of 0.001 mmol/g to 0.1 mmol/g,

producing propylene from a stream comprising butene via metathesis and cracking by contacting the stream comprising butene with the mesoporous silica catalyst and passing the stream comprising butene directly from the mesoporous silica catalyst to the MFI structured silica catalyst, where the stream comprising butene contacts the mesoporous silica catalyst before contacting the MFI structured silica catalyst.

2. The process of claim 1 where the MFI structured silica catalyst has a pore size distribution of at least 1.5 nm to 3 nm.

3. The process of claim 1 where the MFI structured silica catalyst is free of acidity modifiers selected from the group consisting of rare earth modifiers, phosphorus modifiers, potassium modifiers, and combinations thereof.

4. The process of claim 1 where the mesoporous silica catalyst catalyzes isomerization of 2-butene to 1-butene followed by cross-metathesis of 2-butene and 1-butene into a metathesis product stream comprising propylene, and the MFI structured silica catalyst is a cracking catalyst which produces propylene from C 4 or C 5 olefins in the metathesis product stream.

5. The process of claim 1 where the metal oxide of the mesoporous silica catalyst comprises one or more oxides of molybdenum, rhenium, tungsten, or combinations thereof.

6. The process of claim 1 where the metal oxide of the mesoporous silica catalyst is tungsten oxide (WO 3 ).

7. The process of claim 1 where the mesoporous silica catalyst has a molar ratio for silica/tungsten oxide of 5 to 60.

8. The process of claim 1 where the mesoporous silica catalyst includes a surface area of 250 m 2 /g to 600 m 2 /g.

9. The process of claim 1 where the mesoporous silica catalyst has a particle size of 20 nm to 200 nm, and an individual crystal size ranging from 1 to 100 μm.

10. The process of claim 1 where the MFI structured silica catalyst is alumina free.

11. The process of claim 1 where the MFI structured silica catalyst comprises alumina.

12. The process of claim 11 where the MFI structured silica catalyst has a molar ratio of silica to alumina of 200 to 3000.

13. The process of claim 1 where the MFI structured silica catalyst has a surface area of 300 m 2 /g to 425 m 2 /g, and a crystal size of 10 μm to 40 μm.

14. The process of claim 1 where the process achieves at least an 80 mol. % conversion of butene and a propylene yield in mol. % of at least 45%.

15. The process of claim 1 where the MFI structured silica catalyst directly cracks a product of butene metathesis reaction.

16. The process of claim 1 where the mesoporous silica catalyst includes a total acidity of from 0.01 mmol/g to 0.5 mmol/g.

17. A process for production of propylene comprising:
providing a dual catalyst system comprising:
a mesoporous silica catalyst impregnated with metal oxide, where the mesoporous silica catalyst includes a pore size distribution of about 2.5 nm to about 40 nm and a total pore volume of at least about 0.600 cm 3 /g, and
a mordenite framework inverted (MFI) structured silica catalyst that includes a total acidity of 0.001 mmol/g to 0.1 mmol/g, where at least a portion of the MFI structured silica catalyst is in contact with the mesoporous silica catalyst, and

producing propylene from a stream comprising butene via metathesis and cracking by contacting the stream comprising butene with the dual catalyst system, wherein the stream comprising butene contacts at least a portion of the mesoporous silica catalyst before contacting the MFI structured silica catalyst.

18. The process of claim 17 where the mesoporous silica catalyst and the MFI structured silica catalyst are mixed.

19. The process of claim 17 where the mesoporous silica catalyst includes a total acidity of from 0.01 mmol/g to 0.5 mmol/g.

20. A process for production of propylene comprising:
providing a dual catalyst system comprising:
a mesoporous silica catalyst impregnated with metal oxide, where the mesoporous silica catalyst includes a pore size distribution of about 2.5 nm to about 40 nm and a total pore volume of at least about 0.600 cm 3 /g, and
a mordenite framework inverted (MFI) structured silica catalyst directly downstream of the mesoporous silica catalyst, where the MFI structured silica catalyst includes a total acidity of 0.001 mmol/g to 0.1 mmol/g,
where the mesoporous silica catalyst is disposed in a first reactor, the MFI structured catalyst is disposed in a second reactor, and a direct conduit extends between the first reactor and the second reactor, and

producing propylene from a stream comprising butene via metathesis and cracking by contacting the stream comprising butene with the mesoporous silica catalyst and the MFI structured silica catalyst, where the stream comprising butene contacts the mesoporous silica catalyst before contacting the MFI structured silica catalyst.

Assignees

• Saudi Arabian Oil Co
• King Fahd Univ Of Pettroleum & Minerals
• Univ King Fahd Pet & Minerals

Inventors

• Al Khattaf Sulaiman Saleh
• Palani Arudra
• Bhuiyan Tazul Islam
• Shaikh Sohel
• Akhtar Mohammad Naseem
• Aitani Abdullah M
• Al Yami Mohammed A

Classifications

• B01J2229/183

  in framework positions · CPC title

• B01J23/30

  Tungsten · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• B01J29/18 Primary

  of the mordenite type · CPC title

• C07C2529/03

  not having base-exchange properties · CPC title