Multiple-stage catalyst system for self-metathesis with controlled isomerization and cracking

• US 10,550,048 B2
• Filed: 01/17/2018
• Issued: 02/04/2020
• Est. Priority Date: 01/20/2017
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Alshafei, Faisal H., Khokhar, Munir D., Sulais, Noor A., Alalouni, Mohammed R., Shaikh, Sohel K.
• Primary Examiner(s): Mayes, Melvin C.
• Assistant Examiner(s): Patel, Smita S
• Application Number:
  US15/873,421
• Publication Number:
  US 20180208524A1
• Time in Patent Office: 748 Days
• CPC Class Codes: B01J 2235/15 X-ray diffraction
• CPC Class Codes: B01J 23/28 Molybdenum
• CPC Class Codes: B01J 23/30 Tungsten
• CPC Class Codes: B01J 23/36 Rhenium
• CPC Class Codes: B01J 29/035 Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
• CPC Class Codes: B01J 29/40 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 Class Codes: B01J 29/48 containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/34 Mechanical properties
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/617 500-1000 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/638 more than 1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 35/77 Compounds characterised by their crystallite size
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/088 Decomposition of a metal salt
• CPC Class Codes: C07C 11/06 Propene
• CPC Class Codes: C07C 11/08 with four carbon atoms
• CPC Class Codes: C07C 11/10 : with five carbon atoms
• CPC Class Codes: C07C 2/10 : with metal oxides
• CPC Class Codes: C07C 2/12 : with crystalline alumino-silicates or with catalysts comprising molecular sieves
• CPC Class Codes: C07C 2521/08 : Silica
• CPC Class Codes: C07C 2521/12 : Silica and alumina
• CPC Class Codes: C07C 2523/30 : Tungsten
• CPC Class Codes: C07C 2529/035 : Crystalline silica polymorphs, e.g. silicalites
• CPC Class Codes: C07C 2529/40 : of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• CPC Class Codes: C07C 4/06 : Catalytic processes C07C4/025 takes precedence
• CPC Class Codes: C07C 5/2512 : with metal oxides
• CPC Class Codes: C07C 5/2518 : with crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C07C 6/04 : at a carbon-to-carbon double bond
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Embodiments of processes and multiple-stage catalyst systems for producing propylene comprising introducing a hydrocarbon stream comprising 2-butene to an isomerization catalyst zone to isomerize the 2-butene to 1-butene, passing the 2-butene and 1-butene to a metathesis catalyst zone to cross-metathesize the 2-butene and 1-butene into a metathesis product stream comprising propylene and C₄-C₆ olefins, and cracking the metathesis product stream in a catalyst cracking zone to produce propylene. The isomerization catalyst zone comprises a silica-alumina catalyst with a ratio by weight of alumina to silica from 1:99 to 20:80. The metathesis catalyst comprises a mesoporous silica catalyst support impregnated with metal oxide. The catalyst cracking zone comprises a mordenite framework inverted (MFI) structured silica catalyst.

Claims

1. A multiple-stage catalyst system for producing propylene from a hydrocarbon stream comprising 2-butene, the multiple-stage catalyst system comprising an isomerization catalyst zone, a metathesis catalyst zone downstream of the isomerization zone, and a cracking catalyst zone downstream of the metathesis catalyst zone where:

the isomerization catalyst zone comprises a silica-alumina catalyst with a ratio by weight of alumina to silica from 1;

99 to 20;

80, where the silica-alumina catalyst zone isomerizes the 2-butene to 1-butene;

the metathesis catalyst zone comprises a mesoporous silica catalyst support impregnated with metal oxide to form a mesoporous silica catalyst, where the mesoporous silica catalyst zone cross-metathesizes the 2-butene and 1-butene into a metathesis product stream comprising propylene and C₄-C₆ olefins;

the cracking catalyst zone comprises a mordenite framework inverted (MFI) structured silica catalyst, where the cracking catalyst zone cracks the metathesis product stream to produce propylene; and

the MFI structured catalyst is directly downstream of the mesoporous silica catalyst such that the metathesis product stream is passed directly from the mesoporous silica catalyst to the MFI structured silica catalyst.

2. The multiple-stage catalyst system of claim 1 where the isomerization catalyst zone, the metathesis catalyst zone, and the cracking catalyst zone are disposed in one reactor.

3. The multiple-stage catalyst system of claim 1 where the isomerization catalyst zone is disposed in a first reactor, the metathesis catalyst zone is disposed in a second reactor downstream of the first reactor, the cracking catalyst zone is disposed in a third reactor downstream of the second reactor, and a direct conduit extends between the second reactor and the third reactor.

4. The multiple-stage catalyst system of claim 1 where the isomerization catalyst zone is disposed in a first reactor, the cracking catalyst zone is disposed in a second reactor downstream of the first reactor, and the metathesis catalyst zone is disposed in the first reactor downstream of the isomerization catalyst zone with a direct conduit extending between the first reactor and the second reactor or in the second reactor directly upstream of the cracking catalyst zone.

5. The multiple-stage catalyst system of claim 1 where the silica-alumina catalyst includes a surface area of 200 m²/g to 600 m²/g.

6. The multiple-stage catalyst system of claim 1 where the silica-alumina catalyst has a pore volume of at least 0.60 cm²/g.

7. The multiple-stage catalyst system of claim 1 where the silica-alumina catalyst comprises an alumina to silica weight ratio between 1:

99 and 10;

90.

8. The multiple-stage catalyst system of claim 1 where the metal oxide of the mesoporous silica catalyst comprises one or more oxides of molybdenum, rhenium, tungsten, or combinations thereof.

9. The multiple-stage catalyst system of claim 1 where the metal oxide of the mesoporous silica catalyst is tungsten oxide (WO₃).

10. The multiple-stage catalyst system of claim 1 where the mesoporous silica catalyst has a pore volume of at least 0.60 cm³/g.

11. The multiple-stage catalyst system of claim 1 where the MFI structured silica catalyst includes a total acidity of 0.001 mmol/g to 0.3 mmol/g.